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Two-Dimensional Metal-Organic Framework Materials: Synthesis,

Structures, Properties and Applications
Gouri Chakraborty, In-Hyeok Park, Raghavender Medishetty, and Jagadese J. Vittal*

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ABSTRACT: Among the recent developments in metal-organic frameworks (MOFs),

porous layered coordination polymers (CPs) have garnered attention due to their modular
nature and tunable structures. These factors enable a number of properties and applications,
including gas and guest sorption, storage and separation of gases and small molecules,
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catalysis, luminescence, sensing, magnetism, and energy storage and conversion. Among
MOFs, two-dimensional (2D) compounds are also known as 2D CPs or 2D MOFs. Since
the discovery of graphene in 2004, 2D materials have also been widely studied. Several 2D
MOFs are suitable for exfoliation as ultrathin nanosheets similar to graphene and other 2D
materials, making these layered structures useful and unique for various technological
applications. Furthermore, these layered structures have fascinating topological networks
and entanglements. This review provides an overview of different aspects of 2D MOF
layered architectures such as topology, interpenetration, structural transformations, properties, and applications.

CONTENTS 3.3.1. With 2-Connecting Ligands 3779

3.3.2. With 3-Connecting Ligands 3782
1. Introduction 3752 3.3.3. 1D + 2D and 2D + 3D Mixed
2. Design Strategies 3753 Polyrotaxane Structures 3783
2.1. Nomenclature of 2D Nets 3753 3.3.4. Polypseudorotaxane Structures 3783
2.2. 2D Sheets Constructed from 1D CPs 3754 3.4. Interdigitation 3784
2.3. 2D MOFs Based on Different Types of 3.4.1. 1D to 2D Interdigitated Structures 3784
Uninodal Grids 3754 3.4.2. 2D to 2D Interdigitated Structures 3785
2.3.1. 6-Connected Nets 3754 3.4.3. 2D to 3D Interdigitated Structures 3785
2.3.2. 4-Connected Nets 3755 3.4.4. Interdigitation with Mixed Dimensional
2.3.3. 3-Connected Nets 3759 Structures 3787
2.3.4. Another 3-Connected Net: fes 3763 4. Structural Transformations 3788
2.3.5. Another 4-Connected Net: kgm (Ka- 4.1. Dynamic Behavior of Soft Crystals 3788
gomé) 3764 4.2. Transformations Induced by the Removal of
2.3.6. (3,6)-Connected Net: kgd 3765 Coordinating Solvents 3789
2.3.7. 2D Nets Based on Pentagon and 5- 4.2.1. 0D to 1D to 2D Transformations 3789
Connected Nodes 3766 4.2.2. 0D to 2D Transformations 3790
2.3.8. Bilayer or Parquet Floor: kla 3768 4.2.3. 1D to 2D Transformations 3791
2.3.9. Miscellaneous Mixed Grids 3769 4.2.4. 2D to 2D Transformations 3792
2.4. Supramolecular Isomerism in 2D MOFs 3771 4.2.5. 2D to 3D Transformations 3793
3. Different Entanglements 3772 4.2.6. Mechanochemical Reactions 3794
3.1. Interpenetrated and Polycatenated Struc- 4.2.7. 2D to 1D Transformations 3794
tures 3772 4.2.8. 3D to 2D Transformations 3794
3.1.1. 1D to 2D Structures 3773
3.1.2. 2D to 2D Structures 3774
3.1.3. 2D to 3D Structures 3776
Received: September 28, 2020
3.2. 2D MOFs with Mixed Dimensional Frame-
Published: February 25, 2021
works 3778
3.2.1. 1D + 2D to 2D or 3D Structures 3778
3.2.2. 2D + 3D to 3D Structures 3778
3.3. Polyrotaxane Structures 3779

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4.3. Transformations Induced by Heat 3795 6.2.1. With Nanoparticles 3836

4.3.1. 1D to 2D Transformations 3795 6.2.2. With CdSe Quantum Dots and Au
4.3.2. 0D to 1D and 2D Transformations 3795 Nanoparticles 3836
4.3.3. 2D to a 3D Structural Transformation 3796 6.2.3. With Au Nanoclusters 3837
4.4. Structural Transformations by Photochem- 6.2.4. With MXene Phase 3838
ical [2 + 2] Cycloaddition Reactions 3796 6.2.5. With Textiles 3838
4.4.1. 0D to 1D and 2D Transformations 3796 6.2.6. With Layered Double Hydroxide (LDH)
4.4.2. 2D to 2D Transformations 3798 Nanosheets 3839
4.4.3. 2D to 3D Transformations 3799 6.3. Thin Film and Nanosheet Composites of 2D
4.4.4. Stepwise Formation of a MOF from 1D MOFs with Organic Polymers 3839
CP 3802 6.4. Composites with Dyes 3841
4.5. Structural Distortions due to Motion of 6.5. 2D Ordered Colloidal Array 3841
Groups in the Spacer Ligands 3803 7. Summary and Outlook 3841
4.6. Post Synthetic Modifications (PSMs) and Author Information 3842
Reactions 3803 Corresponding Author 3842
4.6.1. Solvent-Assisted Linker Exchange Authors 3842
(SALE) Reactions 3803 Notes 3843
4.6.2. Ligand Replacement/Substitution Reac- Biographies 3843
tions 3804 Acknowledgments 3843
5. Properties and Applications 3804 Abbreviations 3843
5.1. Sorption, Storage, and Separation of Guest References 3844
Molecules 3804
5.1.1. Gate Opening Materials in Interdigi-
tated Structures 3804 1. INTRODUCTION
5.1.2. Sliding and Swelling of the 2D Frame- The discovery of graphene and layered transition metal oxides
work 3805 and chalcogenides along with their novel properties ignited
5.1.3. Role of Pore Functionalization 3805 considerable interest in the research of two-dimensional (2D)
5.1.4. MOF Nanosheets 3808 materials.1−5 When exfoliated into nanosheets of varied
5.1.5. Structural Transformation 3809 thicknesses, the properties of these materials were entirely
5.2. Magnetism 3810 different from their bulk. As such, boron nitride, black
5.2.1. Long-Range Ordering 3810 phosphorus, and metal oxides and hydroxides and layered
5.2.2. Valence Tautomeric Transitions Con- materials of the group IV elements are heavily explored due to
taining Co(III) 2D MOFs 3813 their ability to form layered structures. In the top-down
5.2.3. Spin Crossover (SCO) 3814 approach for these materials exfoliated into sheets, harsh
5.3. Second-Order Nonlinear Optical (NLO) mechanical or chemical conditions are required. The bottom-
Properties 3817 up approach involving direct assembling of metal ions and
5.3.1. Chiral and Achiral Linkers 3817 organic linkers through coordination interactions to fabricate
5.3.2. Donor−Acceptor or Push−Pull Mecha- 2D MOF nanosheets is softer and more controllable for this
nism 3818 purpose. Metal-organic frameworks (MOFs) and coordination
5.4. Luminescence 3819 polymers (CPs) along with the covalent-organic frameworks
5.5. Photochromism and Thermochromism 3821 (COFs) are materials suitable for such approach.6−18 Typically
5.6. Sensing 3823 built with metal nodes and ligand spacers, the metal-organic
5.6.1. Toxic Metal Ion and Anion Sensing 3823 hybrid materials can be extended into various dimensions
5.6.2. Small Molecule and Humidity Sensing 3824 while maintaining their crystallinity. The bottom-up approach,
5.6.3. Nitroexplosives/Nitroaromatics, Am- modular design and construction of structures with tailored
ines, Pesticides, and Antibiotics Sens- properties entice the materials world. With the emergence of
ing 3824 2D materials, it is timely for a comprehensive review on the
5.6.4. Amino Acid and DNA Sensing 3825 synthesis, structure, properties, and applications of 2D CPs/
5.7. Proton Conductivity 3825 MOFs.
5.8. Electrical Conductivity 3826 The metal-ligand coordination bonds have been extensively
5.9. Battery Applications and Supercapacitors 3828 exploited in organizing molecular building blocks into diverse
5.10. Electrocatalysts, HER, and OER 3829 supramolecular architectures leading to 1D, 2D, and 3D
5.11. Catalysis for Organic Synthesis 3829 networks, commonly known as CPs or MOFs.19−41 Apart from
5.11.1. Photocatalysis 3833 general synthetic considerations, crystal engineering of MOFs,
5.12. Miscellaneous Properties and Applications 3833 which involves a careful selection of organic ligands with
6. 2D MOF Composites and Their Applications 3834 appropriate functional groups and metal ions with specific
6.1. Nanocomposites of 2D MOFs with Carbon directionality and functionality, complements a facile path to
Surfaces 3834 make materials of technological importance. It is possible to
6.1.1. With Graphene 3834 design and synthesize 2D sheet structures incorporating
6.1.2. With Graphite 3835 various metal ions and aggregates in the desired oxidation
6.1.3. With C60 and C70 Fullerenes 3836 states, different types of organic spacer ligands for various
6.2. Nanocomposites of 2D MOFs and Hybrid applications.6,42−45 Because of their self-assembly nature, they
Materials 3836 can be made into thin films from solution processing.
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Furthermore, recent advancements in the X-ray crystallo- constructed from triangles (6-connected nodes), squares (4-
graphic techniques have made the characterization of these connected nodes), or hexagons (3-connected nodes). Accord-
crystalline materials easier than ever before. Reflecting these ing to Wells they are called uniform net with the same type of
facts, the number of publications in this area has grown from nodes (uninodal) and polygons, and it is represented by the
130 in 1971−1980 to more than 5930 in 2020, specifically for symbol (n,p), where n is the size of the shortest circuit and p is
the terms 2D CPs and 2D MOFs.46,47 the connectivity of the node. Hence the above nets are
To the best of our knowledge, there is no single represented as (3,6), (4,4), and (6,3) nets, respectively.48−50 In
comprehensive review available in the literature dedicated to reality, the same 2D MOF can have different types of nodes
highlight the overall aspects of 2D MOFs. However, there are and circuits. For example, the net in Figure 1f contains a 3-
several excellent reviews published in the past, dealing with connected node but produced two different sized rings. Schläfli
specific properties and applications combined with 3D symbol is used to represent different sized rings in a net. This
MOFs.7−17 These reviews are very specific highlighting the net is represented by the Schläfli symbol 4.82.54−56 Further, the
individual research laboratories’ contributions and achieve- Schläfli symbol is also used to represent more than one type of
ments. A comprehensive and overall view of various aspects of nodes.57 Recently, three-letter symbols of the Reticular
2D MOFs/CPs will help to benefit the researchers working on Chemistry Structure Resource (RCSR) notation are frequently
2D materials and nanosheets for the use of these 2D MOFs in used to represent the MOF topologies. The complex
numerous device applications. With this purpose in mind, we topologies can be determined with the ToposPro software.58,59
present this review on this emerging area of 2D MOFs. At the In the nets comprising 3-connected, 4-connected, and 6-
outset, we sincerely apologize to the authors for any omission connected nodes, six triangles, four squares, and three
of their excellent publications on 2D MOFs. For consistency, hexagons assemble at a nodal point by making angles of 60°,
we have used the popular name 2D MOFs in this review. 90°, and 120°, leading to topological Schläfli symbols 36, 44,
and 63, corresponding to topology hxl, sql, and hcb,
2. DESIGN STRATEGIES respectively. These are uninodal nets. On the other hand,
The design strategy for the 2D MOFs with a particular when both 3- and 6-connected nodes are joined together, it
topology is concerned with incorporation of required porosity, results in a unique binodal (3,6)-net known as kgd (Kagomé
optical, chiral, catalytic, electrical, and magnetic properties. dual). The four-connected nodes can make angles of 120°, 60°,
This also depends on the metal−ligand ratio, nature of the 120°, and 60° to give rise to either 44 rhombic networks or
metal ions or metal clusters, coordination number, coordina- 3262 based well-known mixed lattices called Kagomé (kgm)
tion geometry and coordination environment, oxidation states, lattice. The combination of such polygons can give rise to
electronic properties, and nature of the organic spacer ligands other types of mixed grids with different connectivity. When
such as rigidity/flexibility, length, shape, geometry, and these symmetry or restraints are lost, then it results in more
functional groups attached to them. complex structures. In addition, the importance of the five
significant edge-transitive 2-periodic nets, hxl, sql, hcb, kgd,
2.1. Nomenclature of 2D Nets
and kgm, in the construction of 3D MOFs by pillaring
It is convenient to describe the MOFs in terms of networks in approach has been summarized by Eddaoudi et al. as well.60
well-known inorganic structures. Net or network, a very useful For 2D motifs, 36 different network topologies have been
method for design and analysis of crystal structures was identified.46 Overall topology of any periodic net can be
developed by Wells48−50 and later extended to coordination analyzed and identified by Systre,61 OLEX,62 and Top-
polymers by Robson and Hoskins.51−53 This powerful osPro58,59,63−67 computer software. For the detailed under-
technique is helpful for the better understanding of the standing of the nets one may refer to a number of excellent
complicated connectivity in MOFs by reducing to simple literatures.47,68−78
networks and topologies. In their review on the topology of 2-periodic coordination
A net is an infinite array of nodes, which are connected by networks, Mitna and Blatov in 2013 found 7083 structures for
linkers (usually the spacer ligands) to make the polymeric the standard representations and 3288 structures for the cluster
structures. A linker will connect two nodes and a node is representations.47 Of these, the square (sql) lattice accounts
connected to two or more links. Some of the common nets for 45% of structures and the honeycomb (hcb) lattice is
encountered in 2D MOFs are shown in Figure 1. These can be observed in 19% cases, followed by fes, kgd, hxl, etc., in less
than 5% each.
It may be noted that the coordination geometry of the metal
ions is lost in the topological description. For example, hcb
topology made of hexagons can also be built from the T-
shaped nodes in addition to the triangular geometrical node
(Figure 2). Both are 3-connected nodes. Hence, honeycomb,
brick wall, and herringbone structures have the same topology
yet they are distinctly different called supramolecular isomers
(see section 2.4).
Similarly, in addition to metal ions with square planar
geometry, tetrahedral or octahedral metal centers can also be
used as 4-connecting nodes for the construction of (4,4) nets.
Further, a 2D sheet with 4-connecting nodes need not contain
only the square type repeating units. The two alternating links
Figure 1. (a−h) Simple and commonly encountered 2D nets along may have different ligands with different lengths as shown in
with their RCSR and Schläfli symbols. Figure 3.79
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Figure 2. Geometrically different but topologically identical nets: (a) honeycomb, (b) brick wall, and (c) herringbone.

network structures. Temperature, time, solvents, concentra-

tion, pH, and impurities determine the outcome of
crystallization. Hence, one has to optimize the experimental
conditions of crystallization to obtain 2D MOFs with the
desired metal−ligand ratio, connectivity, and dimensionality.
A 2D polymeric structure may be flat, undulated, curled,
containing single layer, bilayer, or even more than two but
finite layers. Even if the 2D MOFs are interpenetrated to 3D
Figure 3. A (4,4) net with rectangular shape. structures, they are classified under 2D MOFs. Such intricate
structures are discussed under different shapes of 2D grid
structures in these following sections.
2.2. 2D Sheets Constructed from 1D CPs
2.3. 2D MOFs Based on Different Types of Uninodal Grids
A number of 2D sheets are made from different types of 1D
CPs by interdigitation, interpenetration, or interlocking In this section, the 2D sheets based on their grid shapes are
(Figure 4). These 2D sheets constructed from the 1D CPs classified and discussed. The structures of 2D MOFs
include weaving (woof and weft), fence (chicken) wiring, composed of various types of grids with regular or irregular
interpenetration of normal ladders and step ladders, or polygons of different shapes and sizes.
entangled by various rotaxane-type structures. The first two 2.3.1. 6-Connected Nets. A 6-connected node is suitable
(Figure 4a,b) are due to interweaving, and the last one (Figure for making a triangular hxl net. In this illustration, Hardie et al.
4e) is due to interlocking of 1D strands. They are discussed in employed a hexapodal ligand hexakis(isonicotinoyl)-
section 3 on interpenetration. cyclotricatechylene (hnctc, see Figure 5a) in the assembly of
The 2D MOFs or any other CPs are usually obtained by self- [Re3(hnctc)2Br3(CO)3] and [M3(H2O)6(hnctc)2]·6NO 3·
assembly process. This single-step, one-pot crystallization xDMF (where M = Co(II), Cu(II), or Ni(II)).81 In these
method is a kinetic process and hence experimental conditions two M6L2 motifs are linked together in a pairwise fashion
have greater influence on the formation of coordination through each metal center to give a 6-connected 2D MOF

Figure 4. A few 2D MOFs derived from 1D CPs: (a) Weaving, (b) fence wiring, (c) perpendicular interpenetration of ladders, (d) parallel
interpenetration of step ladders, and (e) polyrotaxane of 1D CPs. (a,b) Reproduced with permission from ref 80. Copyright 2011 Royal Society of
Chemistry.

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(HPMoVI10MoV2O40)] (btx = 1,6-bis(1,2,4-triazol-1-yl)hexane)

with hexacoordinated Co(II) centers exhibits two kinds of
pores, each containing btx and Keggin POM ligands,
respectively, to form a 2D layer.86 Similar related example is
[Zn(tib)(MoO 4 )]·3H 2 O (tib = 1,3,5-tris(imidazol-1-
ylmethyl)benzene).87
Another example of triangular grid 2D MOF has been
observed in [Cd2(H2L)(NO3)(OH)(H2O)2] (H3L = 1H-
tetrazol-5-ylethyl)-amine).88 Here, the 2D sheet comprises a
Figure 5. (a) Chemical structure of ligand hnctc. (b) Crystal structure
[Cd4(OH)2(H2O)2(NO3)2] cluster with 6-connected hxl
of [Re3(hnctc)2Br3(CO)3] MOF with hxl topology. Reproduced with
permission from ref 81. Copyright 2018 Royal Society of Chemistry. topology. A 2D architecture is generated by the metal clusters
formed by bridging of two types of Cd(II) centers via two μ3-
(Figure 5b). The organometallic Re(I) CP is very rare. On the OH− anions and tetrazole ligands that act as a 6-connected and
contrary, [Cu2(hnctc)(TFA)3(isonicotinate)]·xDMF forms a linear nodes, respectively (Figure 8). The flexible nature of the
(3,4,5)-connected topology while [Ag2(hnctc)(DMF)2]-
(BF4)2·2H2O·6DMF generates 3- and 6-connected nodes to
furnish (3,6)-c kgd topology.
Schröder et al. reported a rare and novel 36 tessellated 2D
framework with triangular grids [Zn3(1,4-bdc)3(DEF)2]·DEF
(Figure 6).82 It consists of two types of metal centers: central

Figure 8. 2D sheet structure of [Cd2(H2L)(NO3)(OH)(H2O)2]

along with its view for 6-connected network. Reproduced with
permission from ref 88. Copyright 2016 Royal Society of Chemistry.

V-shaped bis(tetrazole) ligand due to −(CH2)2−NH−

Figure 6. (a) Schematic view of 36 topology net. (b) Projection of the (CH2)2− linkages that provides varied degrees of torsional
structure of [Zn3(1,4-bdc)3(DEF)2]·DEF onto the (100) plane angle and various reaction conditions are also explored, which
showing the architecture of the 36 tessellated 2D sheet. Reproduced are key factors in the building of this type of 2D sheet.
with permission from ref 82. Copyright 2015 Royal Society of
Similarly, a topological net is also observed for the complex
Chemistry.
[Cd3(μ4-bpdc)3(H2O)2]·DMF89 and in a series of isomor-
phous rare-earth metal based 2D MOFs [Ln(BCI)(HCOO)-
Zn(II) center exhibits monodentate binding mode, whereas
(H2O)2Cl] (Ln = Sm, Eu, Gd, Tb, Dy; HBCI = 1,3-
terminal Zn(II) centers possess both monodentate and
bis(carboxymethyl)imidazolium salt (zwitterion)).90
asymmetric bidentate chelating mode. The presence of six-
Huang et al. developed an efficient synthetic and design
connected planar centers with a 60° intercontact angle makes it
strategy of constructing triangular lattices.91 Here, three 2D
an unusual example of 36 connected coordination architecture.
layers with linear trimeric Co3 secondary building units,
Two unique examples based on metal-seamed C-propan-3-ol
[Co3(1,4-bdc)3(5NO2-BIm)2(MeOH)2], [Co3(1,4-bdc)3(5Cl-
pyrogallol[4]arene and C-methylpyrogallol[4]arene macro-
BIm)2]·2MeOH, and [Co3(1,4-bdc)3(5CH3O-BIm)2]·2DMF
cycles with hexameric/dimeric nanocapsules reported by
have been synthesized. The Co3 units display Oh−Oh−Oh
Atwood and co-workers are [Ni24(C40H35O16)6(DMF)2-
(Figure 9a) and mixed Td−Oh−Td (Figure 9b,c) geometries.
(H2O)40] and [Zn(C2O2H3)2(bpy)], respectively (Figure
They explored that the fine tuning of benzimidazole derived
7).83,84 6-Connected [Mg6(-CO2)6(HCO2)6(DMF)6] (named
ligands can result in geometrical frustration and accordingly
as 24-MC-6) metallacrown cluster based 2D MOF,
lead to varied degrees of magnetic ordering from concurrence
[Mg2(HCO2)2(NH2-bdc)(DMF)2] is also found to exhibit
of long-range magnetism and spin frustration to dominant spin
hxl topology net.85
frustration. More examples have been reported in the
POM-based ligands are also found to furnish the triangular
literature.92−97
lattice. For example, the complex [Co2(btx)5-
2.3.2. 4-Connected Nets. The construction of 2D
coordination nets with sql topology can be achieved by the
metal centers and/or the ligands serving as 4-connected node
to generate a (4,4) square lattice nets. This can be executed in
three ways: (i) Combination of octahedral metal centers and
linear rigid and flexible linkers with axial sites occupied by
solvent molecules or counter-anions, (ii) paddlewheel building
blocks with the equatorial sites linked by linear or angular
spacer ligands and the apical sites occupied by terminal ligands
Figure 7. Structures of (a) C-propan-3-ol pyrogallol[4]arene or coordinating solvents, and (iii) tetrahedral metal centers
macrocycle and (b) its 2D Ni-MOF. Reproduced with permission with bent/angular linkers. The first two ways are the most
from ref 83. Copyright 2017 American Chemical Society. common, while the third way is nontrivial. The common
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For this purpose, dipyridyl-based linear spacer ligands such as

pz and bpy and an octahedral metal center acting as a square
planar node with the anions or solvents bonded to the metal
center in a trans-fashion will provide the desired flat 2D sheets.
Indeed, such flat 2D MOFs are widespread in sql nets. For
example, in 1994, Fujita et al. reported a typical flat 2D MOF
[Cd(bpy)2(NO3)2]·1,2-C6H4Br2 as shown in Figure 11.106
However, the use of noncoordinating anions like SiF62− and in
the absence of large cavity filling guest molecules, the same
(4,4) net was found to be interpenetrating.107,108

Figure 9. 36 topology structures and the smallest triangles of (a)

[Co3(1,4-bdc)3(5NO2-BIm)2(MeOH)2], (b) [Co3(1,4-bdc)3(5Cl-
BIm)2]·2MeOH, and (c) [Co3(1,4-bdc)3(5CH3O-BIm)2]·2DMF,
respectively, built by the three Co3 SBUs. Reproduced with
permission from ref 91. Copyright 2019 Royal Society of Chemistry.

shapes of the (4,4) grids are squares and rectangles. However, Figure 11. Typical (4,4) net (sql topology).
rhombus, parallelogram, and other irregular shapes are not
ruled out in these structures. In another 2D MOF [NiL2(NO3)2], a long dipyridyl spacer
2.3.2.1. Flat and Square. Hofmann and Küspert discovered ligand, 4,4′-bis(4-pyridyl)biphenyl (L, shown in Figure 12),
probably the first 2D MOF in 1897,98 and its crystal structure
was determined only in 1952. 99 The structure of
[Ni2(CN)4(NH3)2]·2C6H6 contains Ni2(CN)4 sheets and the
alternate Ni(II) atoms are bonded to two NH3 in trans-fashion.
Hence, the layer has square planar NiC4 cores and octahedral
NiN6 core. The interlayers are sandwiched by benzene
molecules (Figure 10). These benzene molecules can be

Figure 12. (a) Chemical drawing of the ligand L. (b,c) The packing of
the square grids in the presence of two big guest molecules.
Reproduced with permission from ref 109. Copyright 2002 John
Wiley & Sons.

furnished a flat (4,4) net. The use of large guest molecules o-

xylene and mesitylene in the crystallization medium prevented
any interpenetration despite larger square grids with dimension
20 × 20 Å2.109
The influence of guest molecules on the separation of
Figure 10. Structure of Hofmann complex [Ni2(CN)4(NH3)2]· interlayers in [M(bpy)2(NO3)2] (M = Ni or Co) was
2C6H6. Adapted with permission from ref 104. Copyright 2017
investigated by Zaworotko and co-workers. Depending on
Elsevier.
the host−guest stoichiometry, the square grids can pack in
three different packing modes, with the interlayer separation
exchanged with a variety of guest molecules, and these varying in the range 6−8 Å. Further, the guest molecules
compounds are called Hofmann clathrates. Later, a number of interact through noncovalent interactions forming different
new Hofmann-type complexes have been synthesized by types of aggregates.110−112 In many cases, such 2D sheets are
replacing the square planar and octahedral Ni(II) atoms by a overall flat with slight conformational variation. However, they
number of different metal ions.100,101 Later, the ammonia can be considered in this category.113−133
ligands have been replaced by bridging amines and dipyridyl Another report on similar 2D MOFs with square grid
spacer ligands to construct 3D MOFs with interesting paddlewheel synthons describes two isostructural complexes,
magnetic properties.102−104 [Cu(L)NMP)](ClO 4 ), Im-MOF-1 (L = 1,3-bis(4-
Biradha and Fujita reviewed the literature on the flat square- carboxyphenyl)imidazolium; NMP = N-methyl-2-pyrrolidone),
grids in 2003.105 Most of the work on this type of frameworks and [(CuII(LNHC)−CuICl)(NMP)], Im-MOF-2 (LNHC = a
dealt with the influence of guest molecules on interpenetration, carbene form of L) derived from two different copper sources,
nature of adjacent layer packing (AAA, ABAB, etc.), and Cu(ClO4)2 and CuCl, respectively, and imidazolium ligand
interlayer separations. As for the design principles are (Figure 13).134 The latter complex contains CuII due to partial
concerned, flat 2D MOFs can be constructed from straight oxidation of CuI and NHC-CuCl linker generated in situ
and flat spacer ligands as linkers and flat 4-connecting nodes. during the reaction. In both cases, the paddlewheel cluster acts
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Figure 13. (a) Chemical structures of imidazolium ligands. (b)

Simplified framework structures and crystal pictures of Im-MOF-1
and Im-MOF-2. Adapted with permission from ref 134. Copyright
2017 Royal Society of Chemistry.

as a 4-connected node and linker is bent in nature that led to

distorted square segment with each edge dimension 17.578 Å. Figure 15. (a) Double-chain structure formed by the dimer units and
Poriel and co-workers reported non-interpenetrating 2D cpoa2− anions. (b) View of the 2D layer framework and its schematic
MOFs with (4,4) sql net based on spirobifluorene-derived illustration. Reproduced with permission from ref 170. Copyright
2007 Royal Society of Chemistry.
tetracarboxylate ligands and paddlewheel or dimeric units,
both of which act as 4-connected nodes with square planar
geometry and serve as the repeating units.135 In this, three 2D different coordination environment. One Ni(II) is bonded to
MOFs with sql topology were synthesized: [Zn2(L1)(H2O)2]· two L, two bptc ligands, and two aqua ligands. The second
(solv)x (Zn-SBF-1) (H4L1 = 4,4′,4″,4‴-(9,9′-spirobifluorene- Ni(II) is bonded to one L ligand, one bptc and four aqua
2,2′,7,7′-tetrayl)tetrabenzoic acid, Figure 14a), [Zn2(L2)- ligands. Only two of the three carboxylates in bptc are bonded
to Ni(II). Thus, the subtle change in coordination modes of
organic ligand resulted in the formation of this polymeric
structure shown in Figure 16.171

Figure 14. Chemical structures of (a) H4L1 and (b) H4L2.

(DEF)2]·(solv)x (Zn-SBF-2) (H4L2 = 3,3′,3″,3‴-(9,9′-spirobi-

fluorene-2,2′,7,7′-tetrayl)tetrabenzoic acid (Figure 14b), and
[Zn2(L2)(H2O)2]·(solv)x (Zn-SBF-3). Complex Zn-SBF-1
consists of paddlewheel inorganic building units, while the
rest of two complexes contain four-fold zinc dimers.
Interestingly, Zn-SBF-2 complex displays similar rows with
alternating monodentate and bidentate carboxylates along both
the directions of the grid, while Zn-SBF-3 complex shows two
different rows, one with only bidentate and the other with only
monodentate carboxylates along two directions of the grid.
Many other sql nets have been given in the literature.136−169 Figure 16. View of the 2D structure showing rectangular (4,4) net.
2.3.2.2. Rectangular Nets. Rectangular (4,4) nets can be
designed by using a paddlewheel building block and an angular An unprecedented organometallic pentaphosphaferrocene-
dicarboxylate to form 1D chains made up of based 2D MOF [Cu 2 Cl 2 {Cp*Fe(μ 3 ,η 5:1:1 -P 5 )}(μ,η 1 :1-
[M2(dicarboxylate)2] rings, in which the apical positions of C10H8N2)] representing rectangular grid structure has been
the metal(II) centers can be adjoined by dipyridyl spacer reported by Scheer et al.172 It consists of large and small
ligands to complete the rectangular net. For example, the 2D rectangular rings with maximum dimensions 1.14 and 1.51 nm,
MOF [Zn2(cpoa)2(bpee)]·(i-C3H7OH) (H2cpoa = 4-carbox- respectively, comprises two [Cu2Cl2] four-membered rings
yphenoxy acetic acid) is made up of paddlewheel repeating bridged by a pentaphosphaferrocene molecule with the cyclo-
units linked to four carboxylate ligands (Figure 15).170 Two P5 ligand adopting 1,3-bridging mode (Figure 17). On the
cpoa2− anions are bridging the paddlewheel structures to contrary, its constitutional isomer exhibits trapezoidal rings.
produce a 1D chain with rings or loops. This 1D chain is Lee et al. reported a tribenzo-O2S2-macrocycle (p-L) based
further extended by bpee ligands link these 1D chains to 2D MOF [Ag(p-L)ClO4] with tetra- and penta-coordinated
generate a 2D rectangular grid of window size 9.8 × 13.3 Å2, Ag(I) centers bound to bridging ligands with exo-coordination
with layers stacked in an ABAB sequence. mode. The rectangular sheet is puckered with dimensions 11.0
Instead of dicarboxylates, halides can also be used to link × 2.8 Å2 and 11.0 × 7.2 Å2.173 Similarly, a bowl-shaped 12-
octahedral metal centers to form a 1D chain of M2X2. Morsali metallacrown-4 (12-MC-4) subunit derived from Cu(II) ions
and coworkers generated three such rectangular sql nets using and 3-hydroxyisonicotine hydroxamate (hinHA3−) is also
different spacer ligands.79 They are [PbL(μ-L)2(μ-Br)2] (L = utilized for constructing a wavy 2D MOF [CuII(AcO)-
bpy, bpee and bpe). In another example, Py]2[CuII(12-MC-4)] with rectangular voids of 12.6 × 8.9
[Ni3(L)2(bptc)2(H2O)10]·2H2O, the rectangular grid has Å2 dimensions.174
been depicted with mixed ligand strategy (L = 1,4-di(1H- A (4,4) net with two different types of links formed by N,N′-
imidazol-4-yl)benzene) synthesized under hydrothermal con- p-phenylenedimethylenebis(pyridin-4-one) (L) in [Mn(L)4]-
ditions. Two types of octahedral Ni(II) centers bearing (ClO4)2. One type is M-L-M and the second one is a Mn2L2
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coordinated and act as 4-connected nodes to afford a square

grid structure with cavities arranged directly above and below
the adjacent sheets leading to channels, which are orthogonal
to these sheets. This polymer shows sorption properties toward
various gases such as CO2, N2, and H2.
Lin and co-workers reported two 2D Cd(II) MOFs with
rhombic grids by employing a flexible bipyridine ligand affixed
with a free amine moiety.192 Hydro- or solvothermal reaction
conditions in water/ethanol solvent mixtures were imple-
mented to synthesize [Cd(L)2(ClO4)2] and [Cd(L)2(NO3)2]
Figure 17. 2D neutral polymeric framework of [Cu2Cl2{Cp*Fe-
(L = N,N′-(2-pyridyl)-(4-pyridylmethyl)amine). These com-
(μ3,η5:1:1-P5)}(μ,η1:1-C10H8N2)]. Reproduced with permission from
ref 172. Copyright 2018 Royal Society of Chemistry. plexes depict similar structures with bridging L ligand that links
two Cd(II) centers via both 4-pyridyl and 2-pyridyl nitrogen
atoms and ultimately generate the overall architecture as
ring to make this an unusual 4-connected net (Figure 18) with
shown in Figure 20. The introduction of a free amine group
2-fold interpenetration.175 Few other examples on rectangular
grids based 2D MOFs have been reported in the
literature.176−190

Figure 20. View of 2D rhombohedral structure of [Cd(L)2(ClO4)2]

in the ab plane.

demonstrated its ability to undergo intramolecular hydrogen

Figure 18. (a) Chemical structure of ligand and (b) crystal structure bonding with bound anionic species due to which these are
of [Mn(L)4](ClO4)2. Reproduced with permission from ref 175. unapproachable to guest molecules. Apart from the aforesaid
Copyright 1995 John Wiley & Sons. rhombic grid based 2D MOFs, several other examples are also
reported.88,148,177,193−225
2.3.2.3. Miscellaneous 4-Connected Nets. An intriguing Mercuri and co-workers described a series of 2D layered
example of a 2D MOF, (Et4N)2[SnIVCaII(can)4]·2Me2CO dysprosium(III) MOFs constructed with a derivative of 3-
(H2can = chloranilic acid or 2,5-dichloro-3,6-dihydroxy-1,4- chloro-6-cyano-2,5-dihydroxybenzoquinone, a heterosubsti-
benzoquinone), containing a bimetallic square grid with tuted anilate ligand ClCNAn2−, synthesized by employing
unusual node and linkers, has been reported by Robson and varied methods such as layering technique, solvothermal or
co-workers (Figure 19).191 Both Sn(IV) and Ca(II) are octa- conventional one-pot reactions under different reaction
conditions. The complex [Dy2(ClCNAn)3(DMSO)6]·7H2O
obtained via conventional one-pot reaction featured the
example of a flat neutral 2D MOF possessing unusual square
cavities with different dimensions.226 The 2D structure has
square cavities of two different sizes with (8,3) and (4,3)
topology (Figure 21). It exhibits magnetic property due to
weak antiferromagnetic coupling. The other complex obtained
by layering technique exhibits corrugated sheets which will be
mentioned in the next section on 3-connected nets.
A few polyoxo, polyoxometalate, and tetranuclear Cu4S4
Figure 19. (a) Structure of 2D square grid [SnIVCaII(can)4]2− based clusters derived (4,4)-connected 2D nets are observed in
coordination network in (Et4N)2[SnIVCaII(can)4]·2Me2CO and (b) complexes such as [Th6(μ3-O)4(μ3-OH)4(HCOO)12(DMF)2]·
its view down the channels. The pink centers represent Sn and the 10H2O, [Cu2(4-Hdpyp)2(TeMo6O24)(H2O)6]·4H2O (4-dpyp
blue centers Ca. Adapted with permission from ref 191. Copyright = N,N′-bis(4-pyridinecarboxamide)-1,3-propane), and [Cu-
2011 Royal Society of Chemistry. (pzt)] (Hpzt = pyrazine-2-thiol), respectively.227−229 Some
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Figure 21. Structure of [Dy2(ClCNAn)3(DMSO)6]·7H2O: (a) View

of eight- and four-membered rings. (b) View of alternating layers in
the ba plane. Color code: Dy, violet; O, red; Cl, light green; C, black;
N, blue; H, cyan. Adapted with permission from ref 226. Copyright
2019 American Chemical Society.

other similar nets based on macrocyclic and thiacalix[4]arene

units are provided in the literature.167,168,230−232
2.3.2.4. Undulated 4-Connected Nets. A mixed-ligand
strategy has been employed to make undulated sql nets. The Figure 23. (a) ORTEP drawing (at 50% probability) of the
coordination environment of Cd(II) and uranyl ions in UOF-2 with
combination of bis(3-pyridylformyl)piperazine (3-bpfp) and 5- non-H atoms. (b,c) 2D wave-like framework of the UOF-2 viewed
nitroisophthalic acid (H2NIPH) or 3-nitrophthalic acid along b and c directions, respectively. Polyhedra: U atoms, yellow;
(H2NPH) with Cu(II)/Cd(II) centers yielded 2D MOFs, Cd(II) centers, turquiose. Reproduced with permission from ref 234.
[Cu(3-bpfp)(NIPH)(H2O)] and [Cd(3-bpfp)(NPH)(H2O)]· Copyright 2018 American Chemical Society.
H2O, with distorted square pyramidal and pentagonal
bipyramidal geometry of Cu(II) and Cd(II), respectively.233
The first one exhibits a wavy 2D layer with two varied Hard and Soft Acids and Bases rule.235 Another 2D undulated
dimensions of tetranuclear repeating motifs: A (20.53 × 9.57 Cu(I)-halide framework [CuIL] based on a cyclic triimidazole
Å2) and B (19.17 × 12.07 Å2) displaying undulated structure ligand L bearing C3h symmetry has been reported by Carlucci
(Figure 22a). On the other hand, the Cd(II) MOF composed and co-workers, which display corrugated rectangular windows
and exhibit sql topology. It consists of Cu2(μ-X) fragments
with tetrahedral Cu(I) centers and μ2-bridging mode of
ligand.236 Several other related complexes displaying the
common undulated 2D (4,4) network are provided in the
literature as well.178,237−264 Further, a few examples of 2D
(4,4)-connected curled sheets with double helical chains have
also been observed in the literature.265−269
2.3.3. 3-Connected Nets. The hexagonal grid can be
categorized based on its final shape in the framework. These
are honeycomb, brick wall, herringbone (cis-decalin con-
formation), chair-shaped (undulated), and mixed nets (Figure
2). Out of these patterns, the most widely observed form of
hexagon is honeycomb in 2D MOFs. Along with these, a
special form of honeycomb-based framework has been
accounted in the literature with topology termed as kgd
(Kagomé dual) (see section 2.3.6). We will illustrate a few
Figure 22. Stick and simplified representations of the 2D examples related to each type below.
coordination layer structures for (a) [Cu(3-bpfp)(NIPH)(H2O)] 2.3.3.1. Honeycomb: Flat, Cyclohexane-Based, Undu-
and (b) [Cd(3-bpfp)(NPH)(H2O)]·H2O. Adapted with permission lated/Curled. Probably the first honeycomb 2D MOF network
from ref 233. Copyright 2012 Royal Society of Chemistry.
structure was reported by Konnert and Britton in 1966 by
combining two different smallest 3-connecting nodes, namely
of 1D right-handed helical chains in which NPH and 3-bpfp three-coordinate Ag(I) and [C(CN)3]− ligand (Figure 24).270
ligand display bis-chelating and μ2-bridging coordination Because of the thinner size of the nodes, this is two-fold
modes, respectively (Figure 22b). interpenetrated.
A bimetallic uranyl organic framework, [Cd(UO2)(2,2′-
bpdc)2(H2O)2·2H2O] (2,2′-bpdc = 2,2′-bipyridine-4,4′-dicar-
boxylate), features a wave-like 2D MOF designated as UOF-2
(Figure 23).234 It consists of hexagonal−bipyramidal uranium
center, hexacoordinated Cd(II) center and both bidentate and
monodentate 2,2′-bpdc2− carboxylates. In this, both uranyl
centers and [Cd(2,2′-bpdc)2(H2O)2]2− motifs act as 4-
connected nodes resulting into (4,4)-connected sql net.
Complex [Cd(bpdt)2(en)] (H2bpbt = 4,4′-biphenyldithiol)
displays an anionic wave-like rhombic thiolate-based 2D layers
in the presence of alkyldiamine en, in which en plays the dual Figure 24. (a) Schematic view of honeycomb topology and (b)
role of both ligand as well as solvent. Its formation is based on structure of AgC(CN)3.

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Robson and co-workers used a 3-connecting tripodal ligand Other tripodal ligands such as N,N′,N″-tris(4-pyridinyl-
tpt and copper acetate with paddlewheel structure as the linear methyl)-1,3,5-benzene tricarboxamide and tris(4-pyridyl)-
linker to make [{Cu2(O2CCH3)4}3(tpt)2]·2MeOH, which has pyridine, bis(pyrazol-1-yl)(pyridin-4-yl)methane, and 4,4′,4″-
a 2D honeycomb layer with the expected hcb topology (Figure nitrilotribenzoic acid also resulted in 2D honeycomb-based
25).271 The large hexagonal windows of dimension 34−37 Å hexagonal lattice.276−279 Thus, it can be concluded that the
are not interpenetrated due to ABCABC type of stacking of the role of tripodal ligands is crucial in the formation of hexagonal
adjacent layers, stabilized by π···π interactions. grid with honeycomb structure.
The utilization of a unique trigonal metalloligand with C3
symmetry has been demonstrated in the complex [(ML)-
(Rh2 (OAc 4 )) 1.5 ]·xCHCl3 (ML = [Ag(L)(PPh 3)]; L =
hydrotris(3,5-dimethyl-4-(4-pyridyl)-pyrazolyl)borate)) with
honeycomb structure. This is a non-interpenetrating corru-
gated 2D MOF, with ABCABC stacked alternating layers
affected by the distorted trigonal orientation of borate
ligand.280 Wang et al. have reported a 2D honeycomb
architecture with rare tetranuclear starburst clusters [Ag4(μ3-
Cl){S2P(OR)2}3] in the complex [Ag4(μ3-Cl)(dppe)1.5{S2P-
Figure 25. (a) View of the hexagonal window. (b) Honeycomb layers (OR)2}3], where an unusual P-bridging ligand dppe has been
stacked in ABCABC manner. Adapted with permission from ref 271. employed.281 Here, Ag(I) exhibits distorted tetrahedral
Copyright 2000 Royal Society of Chemistry. geometry and six such tetranuclear units are connected
through six dppe ligands in an alternating up and down
fashion to form a 42-atom ring that gets extended to generate
Similarly, another tripodal ligand such as 1,3,5-tris(1- 2D honeycomb net (Figure 27).
imidazolyl) benzene (tib) has also been utilized to achieve
honeycomb structures.272,273 A series of five uranyl 2D MOFs
based on semi-rigid tripodal ligand 1,1′,1″-(benzene-1,3,5-
triyl)tripiperidine-4-carboxylic acid (H3BTPCA) has been
synthesized under solvothermal conditions, studied by Shi
and co-workers.274 This includes [(CH3)2NH2]UO2(BTPCA),
[(CH3)2NH2]UO2(BTPCA), [(CH3)2NH2]2[UO2(BTPCA)]-
[UO2(BTPCA)]·5.5H2O, [(CH3)2NH2]2(UO2)2(BTPCA)2·
3H2O), and [(CH3)2NH2]UO2(BTPCA), which feature
honeycomb nets with varied degrees of distortion affected by Figure 27. (a) Single honeycomb-shaped ring and (b) space-filling
the flexibility of the piperidine ring in the ligand. Among these, model of 2D extended network of [Ag4(μ3-Cl)(dppe)1.5{S2P-
the first three complexes are non-interpenetrated, while the (OR)2}3]. Reproduced with permission from ref 281. Copyright
third and fourth complexes exhibit interpenetration. The part 2005 Royal Society of Chemistry.
of interpenetration is discussed in detail in section 3.
An interesting 2D MOF [Cu(C10H26N6)3(btc)2]·18H2O Another interesting example falling under this type involves
with honeycomb cavity of size 8.7 Å has been reported by Suh a heteroleptic complex based 2D MOF revealed by Hosseini
et al.275 This was synthesized by the self-assembly of Cu(II)- and co-workers.282 The structure consists of trigonal Ag(I)
hexaazamacrocylic complex and Na3btc in H2O/DMSO metal centers coordinated to the para-position of a pyridyl
solvent mixture. A 2D layer with no interpenetration is nitrogen atom and the peripheral nitrile of the acacCN ligand
generated by the coordination of each tetragonally distorted (acacCN = 3-cyanoacetylacetonate) from three different cobalt
Cu(II) centers in the macrocyclic complex to two btc3− in a complexes that led to the formation of homochiral honeycomb
trans-fashion and in turn binding of btc3− to three macrocyclic grid (Figure 28). This has been regarded as the geometrical
units (Figure 26). This polymeric complex can effectively hybrid of homoleptic Co(dpm-4py)3 (dpm = dipyrrin) and
intercalate guest molecules inside its honeycomb cavities such Cr(acacCN)3 complexes reported in the literature.
as phenol. In this process, the honeycomb cavity size of 10.5 Å Recently, Wei et al. reported a set of three isostructural
increased by 2 Å in comparison to its native framework. lanthanoid heteroleptic complexes [Ln2(Q[5])2(GT)(H2O)6]·
4NO3·xH2O (Ln = La, Ce, Nd) (Q[5] = cucurbit[5]uril;
H2GT = glutaric acid) depicting honeycomb topology.283
These consist of two types of nine-coordinated Ln polyhedra
linked by Q[5] via bis-bidentate carbonyl groups on both
sides, forming 1D chains which are further connected by
bridging GT2− ligands to form the 2D net. Hence, this work
provided the pathway to construct novel lanthanoid hetero-
leptic MOFs derived from other Q[n]s with varied structural
diversity and properties. Another complex, [LnNi(dcta)-
(H2O)6](ClO4)·H2O (Ln = La; Nd) (H4dcta = trans-1,2-
Figure 26. Honeycomb net structures in (a) [Cu- diaminocyclohexane-N,N,N′,N′-tetraacetic acid), also features
(C10H26N6)]3[C6H3(COO)3]2·18H2O and (b) its intercalated a undulated honeycomb net based on metalloligand [Ni-
complex. Adapted with permission from ref 275. Copyright 2002 (dcta)]2− that serves as a 3-connected node and linked to a
American Chemical Society. nine-coordinated La(III) atom with distorted monocapped
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Figure 30. (a) Crystal structure of [Cu2(pz)3(CH3CN)2](PF6)·

acetone projected down the c-axis. (b) Hexanuclear copper unit
forming a chair-like structure. (c) Schematic array of infinite sheets.
Reproduced with permission from ref 290. Copyright 1992 American
Chemical Society.

penetrated puckered 2D layer with chair-shaped hexagonal

Figure 28. Honeycomb net structure in the heteroleptic Ag(I)/ layers stacked in ABAB fashion. On the other hand, in
Co(II) 2D MOF. Reproduced with permission from ref 282. [Zn2(deaH)(ndc)1.5]·MeOH (deaH2 = diethanolamine), layers
Copyright 2010 American Chemical Society. are stacked in offset ABCABC fashion (Figure 31a). In

square antiprism geometry to furnish a 3d-4f heterometallic

wavy 2D sheet structure (Figure 29).284 The role of ClO4−
anion is also important to stabilize the overall architecture.

Figure 31. (a) View of the chair-shaped hexagonal window with

schematic view of an offset ABCABC stacking arrangement for (6,3)
Figure 29. Ball-and-stick view of the 2D sheet for [LnNi(dcta)- layers due to the three-fold interpenetration in [Zn2(deaH)(ndc)1.5]·
(H2O)6](ClO4)·H2O representing the honeycomb topology. Adapted MeOH. (b) View of the ship-shaped hexagonal window in
with permission from ref 284. Copyright 2016 Royal Society of [Co2(teaH2)(btb)]·3EtOH. Adapted with permission from ref 291.
Chemistry. Copyright 2015 Royal Society of Chemistry.

An interesting example with this topology is [Cu5(μ4-Br)(μ3- contrast, [Co2(teaH2)(btb)]·3EtOH (btb3− = benzene-1,3,5-
Br)2(μ2-Br)2]5(μ2-MeSPr)3 based on pentanuclear metal tribenzoate) showcases an unprecedented ship-shaped config-
cluster [Cu5(μ4-Br)(μ3-Br)2(μ2-Br)2]5 with capped square uration in hexagonal window to afford ABAB 2D layers (Figure
pyramid geometry and displaying honeycomb 2D sheet.285 31b). In this case, Co2 unit acts as a tripod and central benzene
On the other hand, POMs based honeycomb networks are also ring from btb3− represents as a 3-connected node to generate a
noted in the literature.286−289 Next, we will discuss the binodal hcb net.
complexes with chair-shaped hexagonal frameworks resembling Similarly, in a heterometallic complex [Ni(L)Sm(1,4-
trans-decalin conformation. bdc)1.5]·CH3OH (H2L = salamo-like bisoxime), a chair-shaped
Kitagawa et al. have reported an infinite 2D MOF with pz trans-decalin type hexagonal 2D sheet is featured, which is
ligand and Cu(I) center, [Cu2(pz)3(CH3CN)2](PF6)·acetone, constructed from [Ni(L)Sm] units with distorted octahedral
comprising distorted tetra-coordinated Cu(pz)3(CH3CN) Ni2+ and distorted tricapped trigonal prism Sm3+ metal centers,
subunits.290 Interestingly, the hexanuclear copper unit adopts which are linked via exodentate bdc2− linkers.292 Many other
a chair-like conformation of cyclohexane and eventually forms examples on honeycomb-based hexagonal grids are reported in
a cationic 2D layer with PF6− as counter ions. The sheet is the literature.139,149,206,212,222,226,251,257,293−319
wavy in nature, with large hexagonal cavities inclusive of 2.3.3.2. Brick Wall: Flat and Undulated/Curled. Another
acetone molecules and PF6− above the cavity (Figure 30). In special form of 3-connected net is brick wall structure (Figure
contrast, the methyl substituted pz ligand gave rise to a 1D 32a). In 1995, Fujita et al. reported the first brick wall 2D
chain owing to steric hindrance. This revealed that control over MOF in [Cd(L)1.5](NO3)2 (L = 1,4-bis(4-pyridylmethyl)-
spatial factor is vital for the formation of 2D infinite sheets. 2,3,5,6-tetrafluorobenzene, Figure 32b). Because of the long
Xie and co-workers reported different hexagonal subnets and flexible nature of the ligand, this MOF is triply
with chair shaped windows and dinuclear units.291 Complexes interpenetrated. Interestingly, when non-fluorinated ligand
[Zn 2 (teaH 2 )(ndc) 1.5 ]·MeOH and [Co 2 (teaH2 )(ndc) 1.5 ]· was used, the same M:L stoichiometry furnished ladder 1D
MeOH (teaH3 = triethanolamine) showcase a non-inter- CP, which is its supramolecular isomer.320
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longer edges which are represented by four bpy groups (22.951

Å). The layers arrange in an ABAB fashion and accommodat-
ing the lattice water molecules in between neighboring
layers.323 In another example, [Cu(NCS)2(pn)] (pn = 1,3-
propanediamine), one NCS anion acts as a T-joint bonding to
two Cu(II) bonded via the S atom and the third Cu(II) via the
N atom. The octahedral Cu(II) center also has mer
connectivity of NCS anions, two S atoms and one N atom
along with a chelating pn ligand and a terminal NCS ligand.
This unusual two different T-shaped linkages afforded a brick
wall 2D framework.324 Similar topology was also observed for
[Zn2(L-cys)2(bpy)2(H2O)4]·(H2O)(bpy) (H2L-cys = L-cysteic
acid) with grid size 11.42 × 10.11 Å2 based on Zn···Zn
distance.325 A 2D helical chiral framework, [Ag(CH3CN)4]-
Figure 32. (a) Schematic view of brick wall topology. (b) Chemical
structure of ligand used in [Cd(L)1.5](NO3)2. (c) Triply inter-
[Ag3(CH3CN)8(SiMo12O40)], derived from Keggin-type poly-
penetration in [Cd(L)1.5](NO3)2. (d) 1D ladder-like CP obtained oxoanion [SiMo12O40]4− clusters which are connected to
with non-fluorinated ligand. (c) Reproduced with permission from ref bimetallic units features brick wall topology.326 The crystal
320. Copyright 1995 American Chemical Society. structure of [Ni(azpy)2(NO3)2]2[Ni2(azpy)3(NO3)4]·4DCM
contains unusually two completely different 2D topologies
Usually, three linkers around a metal center with 6- or 7- together, namely (4,4) square grids and (6,3) brick wall layers
coordinate geometry that forms T-shaped connectivity (mer- in the same crystal structure.127
isomer) promotes brick wall structures. In 2.3.3.3. Herringbone: Flat and Undulated/Curled. Her-
[Co2(azpy)3(NO3)4]·Me2CO·3H2O, the coordination geome- ringbone structure has a slight variation from the brick wall
try of Co(II) is a pentagonal bipyramid and three N atoms of structure where half of the rectangular blocks are rotated by
the azpy linkers have mer-geometry to generate the brick wall 90° as shown in Figure 34. This also requires a T-shaped metal
structure.126 For highly corrugated (cyclohexane-like) motifs, a
long flexible spacer ligand such as 1,4-bis(3-pyridyl)-2,3-diaza-
1,3-butadiene can be used along with the nitrate salts of Cd(II)
or Co(II).321 Choi and Suh synthesized both hexagonal and
brick wall type 2D MOFs by changing the experimental
conditions slightly. [Ni(L)3(btc)2]·18H2O (where L is a
macrocyclic ligand) forms brick wall type structure, whereas
[Ni(L)3(btc)2]·14H2O·C5H5N was isolated when pyridine was
trapped as a guest in the crystal lattice (Figure 33).322

Figure 34. Schematic view of herringbone topology.

node and a two-connecting linker ligand. Kitagawa highlighted

subtle influence of the metal ions on the formation of brick
wall and herringbone structures. Reaction of Cd(NO3)2 with
diazopyridine or 4,4′-azobispyridine (azpy) furnished herring-
bone 2D MOF [Cd2(azpy)3(NO3)4]·2Me2CO, while Co-
(NO3)2 yielded brick wall structure.126 Similarly, Proserpio et
al. reported [Cd2(bpethy)3(NO3)4]·DCM and [Cd2(azpy)3-
(NO3)4] to contain undulated herringbone pattern with
parallel three-fold interpenetration.327
Lee and co-workers demonstrated the use of rhodizonate
with nonplanar C2 symmetry as a coordinating ligand for the
construction of 2D MOFs, [Cd(C6O6)(bpym)(H2O)]·H2O
Figure 33. Self-assembly of Ni(II)-macrocyclic complex with btc3− to and [Mn(C6O6)(bpym)(H2O)]·2H2O (bpym = 2,2′-bipyr-
form (a) brick wall and (b) honeycomb frameworks. Adapted with imidine). Owing to bis-bidentate chelating binding modes of
permission from ref 322. Copyright 1998 American Chemical Society.
both ligands with the distorted pentagonal bipyramidal metal
centers, a unique herringbone with cis-decalin type M6
Another example of this kind is [Zn2(PDCO)2(bpy)2- framework is generated (Figure 35).328
(H2O)2]·3H2O (PDCO = pyridine-2,6-dicarboxylic acid N- A 2D MOF, [Zn 2 (ODPA)(bpy)(H 2 O) 3 ]·(H 2 O) 2
oxide) showing a chiral helical 2D layer generated from achiral (H4ODPA = 2,2′,3,3′-oxydiphthalic acid), reported by Meng
{Zn2(PDCO)2} dimer units and bpy linkages. Each brick wall et al. also displays herringbone topology (Figure 36).329 The
is composed of six Zn atoms in which four act as the four structure is based on a flexible bent tetra-carboxylate ligand
vertices while the remaining two behave as midpoints of the ODPA, which binds in a bis(chelating mode) to distorted
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achiral building units, imidazole-4,5-dicarboxylic acid (H3IDC)

and nitrogen-donor linkers, piperazine (prz) and pz.264 These
are similar in structure with (6,3)-connected topology and
contain alternating helical chains connected through parallel
coordination of prz and pz groups leading to achiral nature.
Two unique examples with a similar type of topology have also
been reported recently for [CuXL] (X = I, Br; L = cyclic
trimidazole) in which the ligand L exhibits C3h symmetry. A
2D corrugated chair-like hexagonal sheet is obtained via the
Figure 35. (a) Crystal structure of [Cd(C6O6)(bpym)(H2O)]·H2O Cu2(μ-X)2 dimeric units with distorted tetrahedral Cu(I)
framework. (b) The schematic representation of herringbone type
topology. centers acting as nodes connected to bridging ligands (Figure
38).236 Similar examples on this type of herringbone structural
motifs have been outlined in the literature.235,299,305,323,332−338

Figure 36. (a) Herringbone motif formed by Zn1(cyan)-ODPA and

Zn2(green)-ODPA helices. The two types are of all homochiral
helices (P helix) along the [010] direction. (b) Its topological view. Figure 38. Topological view representing chair-like herringbone
Adapted with permission from ref 329. Copyright 2006 American structure in [CuXL] complex. Reproduced with permission from ref
Chemical Society. 236. Copyright 2019 American Chemical Society.

octahedral Zn(II) centers, and the bpy linker plays a crucial Recently, an interesting synthetic methodology of oxidative
role in strengthening the resulting herringbone motif. addition of iodine to form three 2D undulating MOFs,
Another complex featuring herringbone topology is [Co2(3- [Mn(salen)]2[PtII(CN)4]1−x[PtIV(CN)4(I2)]x (salen = N,N′-
pmntd)3(NO3)4]·2EtOH with a semi-rigid ligand N,N′-bis(3- ethylenebis(salicylideneaminato) (x = 0.18, 0.45, and 0.85),
pyridylmethyl)naphthalene diimide (3-pmntd) and hepta- was investigated and studied the iodine content dependent
coordinated Co(II) centers. The different conformations of structural transformation (Figure 39).339 The I−Pt−I chains
ligand led to the formation of T-type Co(3-pmntd)3 building
blocks and ultimately resulted in butterfly-shaped M6(3-
pmntd)6 unit that extended to afford the non-interpenetrated
2D undulating sheet stacked in an offset fashion.330 In an
anionic zwitterion complex, [Zn2(DDI)3(H2O)2]·I(H2DDII =
4,5-dicarboxy-1,3-dimethyl-1H-imidazolium iodide), contain-
ing a rigid imidazolium ligand H2DDII, a herringbone pattern
is observed (Figure 37).331 This is resulting from a crown-

Figure 39. (a) Cyanide-bridged 2D network structure in the ab plane.

Undulating layer structures and zigzag angles for [Mn-
(salen)]2[PtII(CN)4]1−x[PtIV(CN)4(I2)]x with x = 0.18 in (b), 0.45
in (c), and 0.85 in (d). Color code: Pink (Mn), white (Pt), purple (I),
red (O), blue (N), and gray (C). H atoms are omitted for clarity.
Reproduced with permission from ref 339. Copyright 2019 Royal
Society of Chemistry.

Figure 37. (a) Hexameric crown-shaped macrocyclic ring. (b) formed are perpendicular to the layers and also exhibit
Topological representation of a herringbone. Adapted with inhomogeneity at low temperature. The intermolecular
permission from ref 331. Copyright 2015 Royal Society of Chemistry. interactions through I− and I−Pt−I units leading to
construction of 2D sheets have also been investigated via
shaped hexameric 42-membered macrocyclic unit which spectroscopic studies.
comprises six distorted tetrahedral Zn(II) atoms linked to six 2.3.4. Another 3-Connected Net: fes. Apart from the
and two DDI− in the same and opposite directions, hexagonal net, the 3-connected nodes can also generate 4-
respectively. Further linkage of the remaining carboxylate membered and 8-membered circuits which give rise to the
oxygen atoms with another Zn(II) center generated the overall unusual topology, fes, with Schläfli symbol 4.82 (Figure 40). In
2D architecture. this regard, several 2D MOFs have been reported in the
Lu and co-workers reported a series of achiral 2D MOFs, literature and will be elaborated in this section.
[M(HIDC)(H2O)(prz)0.5] (M = Fe, Mn, Cd) and [Co- Among these, Liu and co-workers synthesized [Cu4(tpbpa)-
(HIDC)(H2O)(pz)0.5], possessing helical chains based on (μ-CN)4] with pseudo-4.82 net topology from CuCN and
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Li[B(bim)4] bearing 3-connected Li sites and dangling bim

groups has been revealed by Feng and co-workers.342 A series
of complexes, [Zn(tib)(BPDS)] (tib = 1,3,5-tris(1-imidazolyl)
benzene; H2BPDS = 4,4′-biphenyldisulfonic acid), [M(μ3-
cppa)(H2O)2] (M = Ni, Co) (Figure 43a) (H2cppa = 4-(3-

Figure 40. Schematic view of the fes topology.

N,N,N′,N″-tetra(2-pyridyl)biphenyl-4,4′-diamine (tpbpa) in a
4:1 ratio (Figure 41).340 Notably, two types of rings are

Figure 43. Topological fes net exhibited by (a)[Ni(μ3-cppa)(H2O)2],

(b) [Zn2(OH)(TZI)(2,2′-bpy)]·H2O, and (c) [UO2(c-chdc)2Ni-
(cyclam)(H2O)]. (a) Reproduced with permission from ref 343.
Copyright 2017 Royal Society of Chemistry. (b) Reproduced with
permission from ref 344. Copyright 2018 Royal Society of Chemistry.
(c) Reproduced with permission from ref 345. Copyright 2018
Figure 41. Structure of (a) [Cu4(tpbpa)(μ-CN)4] and (b) its American Chemical Society.
topological view. Reproduced with permission from ref 340.
Copyright 2012 Royal Society of Chemistry.
carboxyphenyl) picolinic acid), [Zn2(OH)(TZI)(2,2′-bpy)]·
obtained: 18-membered ring [Cu4(CN)2(dpa)2] (A) formed H2O (Figure 43b) (H3TZI = 5-(4-(tetrazol-5-yl)phenyl)-
by two dpa units from two tpbpa ligands and two cyano units isophthalic acid; 2,2′-bpy = 2,2′-bipyridine), [Ni(μ3-cpna)-
linked to four Cu(I) centers and a 30-membered ring (2,2′-bpy)(H2O)]2·H2O, [Ni(μ3-cpna)(phen)(H2O)]·H2O,
[Cu8(CN)6(dpa)2] (B) containing two dpa groups and six [Pb(μ3-cpna)(phen)]·H2O (H2cpna = 5-(4-carboxyphenoxy)
cyano units joined to eight Cu(I) centers. These are alternately nicotinic acid; phen = 1,10-phenanthroline), and [UO2(c-
adjoined with each other such that each A ring is girdled by chdc)2Ni(cyclam)(H2O)] (c-chdc = cis-1,2-cyclohexane dicar-
four B rings and each B ring is further bound by four A rings boxylic acid) also exhibited same (3,3)-connected fes
and four B rings, which ultimately resulted in fes topology with topological net with chair-shaped octagonal ring instead of a
non-interpenetrating layers stacked in ABAB fashion. In such regular shape (Figure 43c).273,303,343−345 In addition, several
types of compounds, non-interpenetration is atypical owing to interesting 2D MOFs with fes topology have been reported in
the occupancy of biphenyl groups in each B ring. The overall the literature.240,311,346−366
2D framework is built up by almost linear (CuCN)n chains The fusion of hexagonal and rhomboidal metallomacrocyclic
with trigonal geometry of metal centers. cages of a Cu(II) complex was investigated by Wen et al.367 It
Complex [Cu(abit)(NO3)]·5H2O (Habit = 4-amino-3,5- is derived from a unique tritopic tris-pyrazine-pillared prismatic
bis(imidazol-1-ylmethyl)-1,2,4-triazole) is another example bicycooxacalixaromatic ligand, L, via the coordination-driven
with similar grid topology which showed a combination of self-assembly process in a 1:1 metal−ligand ratio. The
octagon and rectangular motifs (Figure 42). This complex structure is planar in nature, with rhombic [Cu2(L3)2] and
displayed a unique chair-shaped water tape T4(1)6(1) with hexameric [Cu4(L3)4] cage units (Figure 44). In this 2D MOF,
hexameric and tetrameric cyclic arrangements.341 the metal ions, counterions as well as solvents play significant
Utilizing a boron benzimidazolate tetrahedral anionic ligand, role in determining the resultant topology of the framework.
[B(bim)4]− (bim = benzimidazolyl), a 2D fes net MOF Such complexes exhibit the potential to serve as host
frameworks for the encapsulation of guest species.
2.3.5. Another 4-Connected Net: kgm (Kagomé).
Four-connecting nodes generate not only the sql nets but
also kgm networks. This kgm net is also known as Kagomé
lattice with Schläfli symbol 3.6.3.6. This net comprises triangle
and hexagon circuits as shown in Figure 45.
Zaworotko et al. reported probably the first example of a
Kagomé 2D MOF which is based on a paddlewheel repeating
unit. The prismatic blue-green crystals of [(Cu2(py)2(1,3-
bdc)2)3] were obtained by diffusion of ethanolic Cu(NO3)2
Figure 42. (a) Structure of 2D coordination network in [Cu(abit)- solution into a solution of 1,3-bdc, py, nitrobenzene, 1,2-DCB,
(NO3)]·5H2O. (b) Its topological view. Reproduced with permission or naphthalene in ethanol. The 4-connected paddlewheel
from ref 341. Copyright 2012 Royal Society of Chemistry. structures were linked by the 1,3-bdc spacer ligand.368 The
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2,5-PDC is coordinated to two In(III) atoms by forming a five-

membered ring by an N- and O-chelation and the O in the 5-
position by monodentate fashion. The assembly of the 4-
connected repeating units generating three- and six-membered
rings resulted in the overall kgm topology as shown in Figure
46b.
Cheng and co-workers have investigated a series of
lanthanide MOFs out of which two complexes, [Pr3(Hnica)6-
(H2O)9]·3H2O·SO4·NO3 and [Nd3(Hnica)6(H2O)9]·3H2O·
SO4·NO3 (Hnica = 2-hydroxynicotinic acid), exhibit wavy
2D structure with Kagomé (kgm) net (Figure 47).195 These

Figure 44. (a) The rhomboidal and (b) hexagonal cage motifs. (c)
The overall 2D polymeric network structure. Reproduced with
permission from ref 367. Copyright 2013 American Chemical Society.

Figure 47. 2D kgm lattice structure exhibited in

[Pr3(Hnica)6(H2O)9]·3H2O·SO4·NO3. Reproduced with permission
from ref 195. Copyright 2008 American Chemical Society.

complexes are isostructural in nature with the metal centers

adopting moderately contorted monocapped square antiprism
geometry coordinated to bridging μ1,3-COO groups from
Hnica− ligand. In case of Pr(III)-based 2D MOF, the
hexagonal ring exhibits a diameter of 12.481 Å with each
edge specified by 6.258 Å of Pr···Pr distance and pores
occupied by lattice NO3− and SO42− groups.
Figure 45. Schematic view of Kagomé (kgm) topology. Similarly, complexes [Cu(L1)0.5(BIE)] (H4L1 = 1,2,4,5-
benzene tetracarboxylic acid; BIE = 2,2′-bis(1H-imidazolyl)-
ether), [Co(L2)(biim-5)]·3H2O (H2L2 = 1,3-benzenedicarbox-
magnetic properties of this compound is described in the ylic acid; biim-5 = 1,1′-(1,5-pentanedidyl)bis(imidazole)) and
section 5.2.1.3. Under different experimental conditions, they (H3O)[Cu3(tbip)3.5(H2O)2]·H2O (H2tbip = 5-tert-butyl iso-
also obtained a 2D MOF with square topology.369 Another phthalic acid) display kgm lattice with 4-connected node of
derivative of 1,3-bdc, namely, 5-benzyloxy-1,3-bdc, also distorted octahedral Cu(II), tetrahedral Co(II) centers and
produced Kagomé 2D lattice with interesting sextuplet phenyl distorted trigonal bipyramidal with paddlewheel mo-
embrace between the first and third layers.370 tifs.299,372,373 In the next section, we will discuss some selected
Eddaoudi et al. described the formation of a Kagomé 2D binodal nets.
framework formed by 4-connected building units using 2,5- 2.3.6. (3,6)-Connected Net: kgd. This unique (3,6)-
PDC (Figure 46a).371 In [In(2,5-PDC)2]·HTMDP·EtOH· connected binodal net topology shown in Figure 48 is known
2H2O (HTMDP = 4,4′-trimethylenedipiperdine), the octahe- as kgd (Kagomé dual) with the Schläfli symbol (43)2(46).
dral In(III) center is coordinated to two nitrogen atoms and Despite having two different connecting nodes, this net
four oxygen atoms of four independent 2,5-PDC ligands. Each contains only rhombus shaped circuits.
The ligand 1′,2′,3′,4′,5′,6′-hexakis(4-carboxyphenyl)-
benzene (H6L) has been used successfully to synthesize two
2D MOFs, [Co4Cl2L] (Figure 49) and [(CH3)2NH2]2[Co2L-
(H2O2], with kgd topology using [Co2(-COO)3Cl] and [Co2(-
COO)3(OH2)] clusters as 3-c building blocks.374 The BET
surface area of 1299 m2 g−1 for the neutral MOF has been
reported at 87 K with narrow pore size distribution, centered at
6.9 Å. Further H2 and CO2 uptake has been measured as 209.9
cm3 (STP) g−1 and 106.8 cm3 (STP) g−1 at 77 K/1 bar and
Figure 46. (a) Illustration of the repeating unit InN2(CO2)4, viewed 273 K/1 bar, respectively. The same ligand furnished the
as a 4-connected node, and (b) a schematic representation of the expected kgd topology in [Ni2(L)]·4H2O with the building
Kagomé lattice. Adapted with permission from ref 371. Copyright block [Ni(-COO)3], in which the oxidation state of Ni is 3+,
2005 American Chemical Society. whereas Mg(II) and Cu(II) compounds yielded 3D MOFs.375
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Figure 48. Schematic representation of kgd topology.

Figure 50. Topological view with kgd net in complex [Ru(Cp)-

(C6H6)][K{C(CN)3}2]. Adapted with permission from ref 377.
Copyright 2019 John Wiley & Sons.

Figure 49. Combination of 3-c dinuclear Co2(-COO)3Cl clusters and

the 6-c hexagonal ligand H6L, lead to the construction of the layered
[Co4Cl2L] with kgd topology. Adapted with permission from ref 374.
Copyright 2017 Royal Society of Chemistry. Figure 51. (a) Chemical structures of bpib and H2L ligands. (b) Ball-
and-stick representation of the sheet-like structure of
[Zn5(bpib)2(L)4(OH)2(H2O)2]. (c) Its topological view and (d)
A Pb(II) complex [Pb2(bpdado)Cl2(H2O)2] (H2bpdado = ball-and-stick representation of interlocked nets. Adapted with
2,2′-bipyridine-3,3′-dicarboxylate-1,1′-dioxide) represents a permission from ref 378. Copyright 2008 American Chemical Society.
wavy kgd framework with distorted octahedral and pentagonal
bipyramidal Pb(II) centers in which metal centers behave as 3-
connecting nodes and bpdado ligands as 6-connected nodes.376
An organometallic 2D MOF, [Ru(Cp)(C6H6)][M{C(CN)3}2]
(M = K, Rb) (Cp = C5H5), constructed from organometallic
ionic liquid components [Ru(Cp)(C6H5R)][C(CN)3] and
anionic part [M{C(CN)3}2]− anion displayed cationic
sandwiched structures with winding 2D sheet with kgd
topology. This is due to rotational disorder at the Cp and
C6H6 rings present in the cationic molecule (Figure 50).377
[Zn5(bpib)2(L)4(OH)2(H2O)2] (bpib = 1,4-bis(2-(pyridin-
2-yl)-1H-imidazol-1-yl)butane; H2L = 3,3′-methylenebis(oxy)- Figure 52. Structure of [Zr6(μ3-O)4(μ3-OH)4(BTB)2(OH)6(H2O)6]
dibenzoic acid) provides a highly corrugated kgd net which is with Zr6 cluster. Reproduced with permission from ref 379. Copyright
two-fold parallel interpenetrated (Figure 51).378 2015 American Chemical Society.
Matzger et al. reported a unique non-interpenetrated cluster-
based 2D MOF [Zr6(μ3-O)4(μ3-OH)4(BTB)2(OH)6(H2O)6],
derived from a tritopic linker BTB (1,3,5-(4-carboxylphenyl)- shown below.48 The first two types require a combination of 3-
benzene) in the presence of concentrated HCl and exhibits and 4-connecting nodes, whereas the third type is formed by a
kgd topology net (Figure 52).379 A few other related examples combination of 3-connected and 6-connected nodes (Figure
on kgd topology in 2D MOFs are noted in the 53). The first type with pentagonal tiling, called Cairo tiling,
literature.380−388 containing a row of 4-connected nodes alternates with the 3-
2.3.7. 2D Nets Based on Pentagon and 5-Connected connected nodes (Figure 53a).
Nodes. In the 2D framework structures, three-, four-, and six- The first periodic tiling of pentagons in layered MOFs was
sided polygons are common. Incorporation of five-sided reported by Zaworotko et al. in 2001. In [(Cu2(μ2-
polygonal circuits has not been explored extensively. Fourteen O2CCH2CH3)4)5(HMTA)3] (HMTA = hexamethylenetetr-
different types of convex pentagons can tile the plane although amine), three of the four N atoms of the tetrahedrally disposed
a regular pentagon cannot tile the plane.389−391 Of these, three HMTA are connected alternatively by the linker Cu2(μ2-
duals of the eight semiregular nets are pentagonal tilings as O2CCH2CH3)4 (Figure 54).392 The 3- and 4-connected
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eclipsed manner to generate pentagonal channels with 11.2%

solvent accessible volume.393
A similar pentagonal layer has been found in an anionic 2D
MOF. In the solid-state structure of (NH4)3[In3Cl2(bpdc)5],
one In(III) is eight-coordinated and binds to four different
bpdc ligands to form a 4-connected node (Figure 56).353 The

Figure 56. Pentagon monolayer connection in-

Figure 53. (a−c) The nets that are duals of three semiregular nets (NH4)3[In3Cl2(bpdc)5].
and which represent three of the 14 tilings that contain congruent
pentagons.
other two In(III) centers act as a 3-connected node with a
HMTA produced this interesting periodic tiling of pentagons terminal chloride ion and three chelated carboxylate groups.
with (5,43)-network. Because of the long spacer ligand and undulated nature, this is
two-fold interpenetrated in parallel. Further, this MOF is found
to be an efficient catalyst for the coupling of CO2 with a series
of terminal epoxides to produce cyclic organic carbonates
selectively.
Shore et al. reported an interesting special type of
pentagonal tiling called Cairo tiling (MacMahon’s net, RCSR
code mcm with a short Schläfli symbol, {53}2{54.82}) in a few
2D MOFs [Ln(DMF)4Cu2(CN)5] (Ln = La, Gd, Er) and
[Gd2(DMF)8Cu4(CN)10] (Figure 57a).394,395 In this structure,
the pentamer has Ln2Cu3 cores bridged by CN ligands with
two Cu(I) atoms are linked through a cyanide bridge. The

Figure 54. Crystal structure of [(Cu2(μ2-O2CCH2CH3)4)5(HMTA)3]

with pentagonal tiling.

Another 2D MOF [Zn2(im)Cl2{B(im)4}] (im = imidazo-

late) shown in Figure 55 contains only pentagonal rings. This
unusual (3,4) connected pentagon layers are stacked in the

Figure 55. (a) The mcm net in [Zn2(im)Cl2{B(im)4}]; the im Figure 57. (a) Structure of [Gd2(DMF)8Cu4(CN)10] showing a
ligands are highlighted as red lines. (b) The eclipsed stacking of the single layer. DMF ligands are omitted for clarity. (b) View of the
mcm-type layers, generating pentagonal channels (one is highlighted Cairo tile. (a) Adapted with permission from ref 395. Copyright 2015
as a red pentagon). Reproduced with permission from ref 393. John Wiley & Sons. (b) Reproduced with permission from ref 394.
Copyright 2010 Royal Society of Chemistry. Copyright 2015 American Chemical Society.

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Cu(I) atoms are 3-connected and Ln(III) atoms are 4- with tetrahedral geometry acts as a 4-connected node, while
connected. Interestingly, all of the 4-coordinated Ln(III) Co(II) ion exhibits octahedral geometry with a 5-connected
centers are in a row and all of the Cu(I) centers occupy node. As depicted in Figure 59 both of these consist of fused
alternate rows in the pentagon tiling. Such Cairo tiling hexagonal and rhombic polygons with different connectivity to
structures (Figure 57b) has also been observed in other 2D generate a mixed grid structure. Therefore, the increment of
MOFs.396−399 flexibility in the ligands influenced the different topological net.
Now we will discuss the nature of 2D MOFs that can be 2.3.8. Bilayer or Parquet Floor: kla. The bilayers also
obtained from 5-connected nodes. A 5-connected 2D frame- called “parquet floor”, are formed when two coordination
work has been shown to result in cem topology by LaDuca and polymeric layers interact through coordination bonds to form a
co-workers. 4 0 0 The compound [Co(1,2-phda)(4- stable structure. One way of designing is to pack two layers of
bpmp)1.5(H2O)](H24-bpmp)0.5(ClO4)·12H2O (1,2-phda = 1D ML chains at right angles and joined by bridging the metal
phenylene-1,2-diacetate, 4-bpmp = bis(pyridylmethyl)- centers by another spacer ligand L (Figure 60). Typically, it
piperazine) has trigonal bipyramidal Co(II) node, connected has the M:L ratio of 2:3 if same linker ligands are used.
by three 4-bpmp ligands in the equatorial plane and two
oxygen atoms of the 1,2-phda ligands (Figure 58). This
generates trigonal and square lattices alternatively to produce
the cem net with Schläfli symbol (33.44.53).

Figure 60. Schematic diagram of parquet floor.

Such a packing requires a T-shaped nodes as in the case of

brick wall structures with metal centers preferably in
pentagonal bipyramidal geometry as in the 2D MOFs
[M2(bpy)3(NO3)4]·xH2O (M = Co(II), Ni(II), and Zn(II)).
The sorption of CH4, N2, and O2 have been investigated in
these interpenetrated bilayer MOFs by Seki and co-workers.404
Different spacer ligands and metal ions have also been used for
this purpose.405−407 There are many other ways of mending
two layers by coordination bonds. Some of the unusual bilayer
Figure 58. (a) 5-connected cationic layer in [Co(1,2-phda)(4- structures with mixed-linkers are described below.
bpmp)1.5(H2O)](H24-bpmp)0.5(ClO4)·12H2O. (b) Framework per- Suh et al. have reported a sponge-like behavior in a 2D MOF
spective of the cem Archimedean network. The type A and type B 4- with bilayer motif for the reversible uptake of guest
bpmp ligands are represented as green and purple bars, respectively. molecules.408 The bilayer structure [Ni2(C26H52N10)]3[btc]4·
The 1,2-phda ligands are drawn as red bars. Reproduced with 6C5H5N·36H2O was assembled from dinickel(II) bismacrocy-
permission from ref 400. Copyright 2010 Royal Society of Chemistry. clic complex [Ni2(C26H52N10)(Cl)4]·H2O and Na3btc (Figure
61a,b). Each Ni(II) atom was bonded to btc in trans fashion,
A similar topology was reported in another 2D MOF,
[Zn3(HL)(1,4-bdc)3] (HL= 3,4-bis(pyridin-4-ylmethoxy)-
benzoic acid), in which Zn3 clusters act as 5-connected
nodes.401 Similar 5-connected nodes are also present in other
2D MOFs.402 Using flexible bis(imidazole) ligands, 1,4-
bis(imidazol-1-ylmethyl)benzene (L 1 ) and 1,1′-(1,4-
butanediyl)bis(imidazole) (L2) two complexes [Zn2(L1)-
(Hbtc)2]·2H2O (Figure 59a) and [Co(L2)(Hbtc)] (Figure
59b) have been synthesized hydrothermally.403 These
displayed (3,4) and (3,5)-connected net with Schläfli symbols
{42·6}{42·64} and {42·6}{42·68}, respectively. Zn(II) center

Figure 61. (a) X-ray structure of dinickel(II) bismacrocyclic complex.

Crystal structures of (b) [Ni2(C26H52N10)]3[btc]4·6C5H5N·36H2O,
Figure 59. Schematic description of (a) the (3,4) and (b) the (3,5)- (c) [Ni 2 (C 2 6 H 5 2 N 1 0 )] 3 [btc] 4 ·20C 5 H 5 N·6H 2 O, and (d)
connected mixed 2D nets, respectively. Reproduced with permission [Ni2(C26H52N10)]3[btc]4·14C6H6·19H2O. Adapted with permission
from ref 403. Copyright 2008 American Chemical Society. from ref 408. Copyright 2002 American Chemical Society.

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and each btc ligand was bonded to three different Ni(II) atoms
forming T-shaped geometry. The p-xylyl groups in the ligand
act as pillars to form the bilayer structure. The structures
obtained by exchanging guest water molecules with pyridine
and benzene also afforded bilayer structures, [Ni 2 -
(C26H52N10)]3[btc]4·20C5H5N·6H2O and [Ni2(C26H52N10)]3-
[btc]4·14C6H6·19H2O, respectively (Figure 61c,d)
Another reversible sponge-like dynamic behavior in a bilayer
2D MOF was reported by Kitagawa et al. in [Cu(pydc)(bpp)]·
5H2O (pydc = pyridine-2,3-dicarboxylate).409 A honeycomb
layer was formed by Cu(pydc)(bpp)0.5, and the other half of
the bpp connects another honeycomb layer as a “pillar” to
complete the bilayer structure. The guest water in the lattice
can be lost in a SCSC manner. The activated MOF shows
some interesting gate-opening phenomenon for certain gases Figure 62. View of 2D grid in [Zn2(tpt)2(btec)]·2H2O.
and solvents.
In [M2(C5O5)(anti-bpee)(gauche-bpee)], (M = Mn(II),
Fe(II), and Cd(II); C5O5 = croconate dianion), two of the
brick wall layers formed by [M(μ3-C5O5)0.5(μ4-C5O5)0.5(anti-
bpee)0.5] are cross-linked by gauche-bpee ligands to form the
bilayer structure.410 The role of bpee is very similar to what
Zaworotko observed before.406 The tetracarboxylate ligand,
biphenyl-3,3′,4,4′-tetracarboxylate (bptc) seems to favor
bilayer structures with Zn(II) in the presence or absence of
1,2-bis(4-pyridyl)ethane.411 Similarly another tritopic ligand,
4-(pyridine-3-yl)isophthalate (L), forms a bilayer 2D MOF
with Cd(II). The 3-pyridyl groups helps to mutually connect
two layers formed by Cd(carboxylate)2 moiety in [Cd(L)-
(H2O)]·H2O.412 The ligand 4′-(1H-tetrazol-5-yl)-[1,1′-bi- Figure 63. (a) Crystal structure of [Cu2(tpt)2(H2btec)]. (b) View of
phenyl]-3,5-dicarboxylate has also been successfully utilized 2D double-layer topologic structure. (c) View of tpt-Cu layer. (d) 2D
to construct bilayer 2D MOF.413 double-layers interpenetrate into 3D structure (each color represents
Two different types of bilayers have been reported for the a double-layered piece). Reproduced with permission from ref 414.
Zn(II) and Cu(II) 2D MOFs having the same chemical Copyright 2008 American Chemical Society.
formula. These are not strictly considered as supramolecular
isomers, but the influence of the metal ions on the connectivity two outer layers via oxygen atom of the IN ligands. In the top
of the 2D MOF is highlighted. In the 2D MOF, and bottom layers, the square pyramidal Cu(II) center with
[Zn2(tpt)2(btec)]·2H2O (H4btec = 1,2,4,5-benzenetetracar- CuN3O2 core, is bonded to four IN ligands, two pyridyl N
boxyic acid), Zn2(btec) forms a 1D chain structure with each atom, and two oxygen atoms, and the apical position is filled by
carboxylate acts as a monodentate ligand, bonded to four another pyridyl N atom from the inner layer. The 2D MOF is
different Zn(II) atoms.414 In a rare case, only two of the three double interpenetrated.
pyridyl N atoms in (tpt) ligand are bonded to Zn(II) with Mir et al. described another bilayer structure. In the 2D
ZnN2O2 core tetrahedral geometry. Interestingly tpt ligands MOF [Zn2(aip)2(bpy)(H2O)2]·2MeOH (aip = 5-aminoisoph-
from adjacent Zn(II) atoms are not connecting to the same thalate), the square pyramidal Zn(II) atom is bonded to an
Zn(II) atoms in the adjacent Zn2(btec) chains but connecting aqua ligand, an oxygen atom of aip, an N atom of the amino
different Zn2(btec) chains, one above and another below, to group, and a N from bpy in the equatorial basal plane.416 The
form a bilayer-type of 2D MOF structure (Figure 62). This oxygen atom of another aip anion occupies the apical position.
structure has rectangle repeating units with hexagonal channels The aip anion in turn connected three different Zn(II) atoms.
in the bilayer structure. The connectivity of [Zn(-COO)2(NH2-)] created a corrugated
Whereas the corresponding Cu(II) forms honeycomb layer, and two such layers are connected by the bpy to generate
bilayer. In [Cu2(tpt)2(H2 betc)], Cu(tpt) forms the expected the bilayer structure. Many 2D nets with bilayered structures
honeycomb structure.414 H2btec acts like 1,4-bdc ligand linking have been investigated in case of POM-based frameworks.289
two Cu(tpt) layers, bonded to Cu(II) in a monodentate Several more examples for bilayers can be found in the
fashion, so that the Cu(II) has a rare trigonal pyramid literature. Many of them are interpenetrated.307,417−428
coordination geometry. The overall structure is a bilayer made 2.3.9. Miscellaneous Mixed Grids. Apart from those
up of honeycomb network structures (Figure 63). Because of commonly occurring nets discussed in the previous sections, a
the large cavity in the honeycomb structure, it is triply variety of mixed-connected 2D nets have been extensively
interpenetrated. covered in the recent reviews and books.46,47,56 Hence, only a
An unusual triple-layer 2D MOF has been reported by Lu few selected examples have been illustrated in this section.
and Babb by the use of isonicotinate (IN) and trans-bpee A series of complexes based on ether-bridged tritopic bent
ligands with Cu(II).415 In the crystal structure of [Cu3(bpee)- carboxylic acid, 2-(2-carboxyphenoxy)terephthalic acid
(IN)6(H2O)2], the middle layer is not strictly a 2D layer, but a (H3cpta), has been exemplified by Kirillov and co-workers.429
linear coordination polymer, Cu(bpee) with the octahedral Among these, the compounds with mixed 2D net topology was
Cu(II) center bonded to two aqua ligands and connected to observed for [Mn 3 (μ 5 -cpta) 2 (2,2′-bpy) 2 ], [M 3 (μ 4 -
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Figure 64. Schematic representation of different mixed grid 2D nets based on H3cpta and auxiliary ligands. Adapted with permission from ref 429.
Copyright 2017 Royal Society of Chemistry.

cpta)2(phen)3(H2O)2] (M = Mn, Cd), [Cd2(μ4-cpta)(μ-

Cl)(phen)2], [Cd3(μ5-cpta)2(phen)2(H2O)2], and [Cd3(μ5-
cpta)2(H2biim)2] (H3cpta = 2-(2-carboxyphenoxy) tereph-
thalic acid; H2biim = 2,2′-biimidazole) (Figure 64). Complex
[Mn3(μ5-cpta)2(2,2′-bpy)2], comprised trimetallic Mn3 unit in
which two types of Mn(II) with a hexa-coordination
environment, are involved which are bridged by μ-bridging
bidentate and tridentate carboxylate moieties to form a (3,4,5)-
connected net with point symbol {43}2{44·86}2{45·6}. In the
case of [M3(μ4-cpta)2(phen)3(H2O)2] (M = Mn, Cd), the Mn3
subunit comprises distorted octahedral and square pyramidal
metal centers interlinked by μ4-cpta3− ligand to generate a rare
3,4L128 topology with point symbol {3·92}{32·4·92·10}. On
the other hand, [Cd2(μ4-cpta)(μ-Cl)(phen)2] exhibits a rare
(3,3,4)-connected 3,3,4L29 topology with point symbol {3 ·
102}{3·4·5 · 102·11}{3·4·5}, where the distorted octahedral
Cd(II) centers behave as 3-connected nodes and carboxylate
ligand as a 4-connected node. On the contrary, [Cd3(μ5-
cpta)2(phen)2(H2O)2] and [Cd3(μ5-cpta)2(H2biim)2] resem-
ble similar structure involving distorted octahedral Cd(II) Figure 65. (a−h) Topological views of the 2D layered structures of
centers and μ5-cpta3− ligand with the only difference in the phosphonate complexes. Adapted with permission from ref 430.
Copyright 2018 Royal Society of Chemistry.
terminal auxiliary ligand and therefore exhibit same topological
net with (3,4,5)-connected nodes.
Another set of compounds based on phosphonic acid ligand, metal centers and connectivity. It is composed of both
p-F-C6H5-CH2-N(CH2PO3H2)2, (H4L), were also reported to distorted octahedral and trigonal bipyramidal Fe(III) sites and
display mixed grid structures.430 These include [Co3(HL)2- tridentate/bidentate phosphonate groups that form
(H2O)4]·2H2O, [Cu(H2L)H2O], and [Fe3(L)2(H2O)3OH]· [Fe3(P2O4)2] units and overall framework exhibits (3,4,4)-
2H2O in which the 2D layers are observed to possess metal connected trinodal net with 8- and 12-membered rings present
ions and PO3 groups arranged in a regular and alternating in it (Figure 65f−h). Only complex [Cu(H2L)H2O] was
fashion. The first complex is a wavy 2D sheet composed of observed to show weakly ferromagnetic properties.
[Co3(P2O5)2] units with distorted octahedral Co(II) sites and Complex [Co4(DPDBT)5(fuma)4(H2O)2](NO3)4(H2O)7
tridentate/bidentatephosphonate groups. The layer is formed (DPDBT = 2,8-di(pyridin-4-yl)dibenzo[b,d]thiophene; fuma
by 4-, 8-, and 12-membered rings adjoined together alternately = fumarate dianion) features a trilaminar 2D network in which
to generate a (3,4,6)-connected trinodal net (Figure 65a−c). trinuclear [Co3(COO)4]5+ cluster and Co(3) atom act as 6-
In complex [Cu(H2L)H2O], the phosphonate groups adopt connected and 4-connected nodes, respectively, to generate a
monodentate and tridentate coordination modes with (4,6)-connected gek2 net with Schläfli symbol {32.44}-
distorted octahedral Cu(II) center to produce [CuP2O4] {34.42.64.75} (Figure 66).431
inorganic units that generate the 2D layer with 8- and 16- A MOF with the connectivity of 10 has been reported. The
membered rings (Figure 65d,e). Complex octanuclear Co(II) cluster in [Co 8 (DCPPT) 6 (μ 3 -
[Fe3(L)2(H2O)3OH]·2H2O is slightly different from the OH)4(H2O)4]·5H2O (DCPPT = 1-(3,5-dicarboxyphenyl)-4-
other two with respect to the coordination geometry of phenyl-1H-1,2,3-trizole), is a 10-connected node and the
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1,2,4-triazole) derived from a rare tetragonal prism-like Zn8

cluster is also reported. In this complex, metal cluster acts as
12-connected nodes and dicarboxylate as 3-connected
nodes.433 Many other 2D MOFs with mixed grid architectures
formed by the fusion of different polygons are observed in the
literature.241,336,434−446
2.4. Supramolecular Isomerism in 2D MOFs
Isomerism, well known in organic and inorganic chemistry, is
the phenomenon in which a compound with the same
chemical formula will have different chemical structures.
Zaworotko has extended this concept to account for the
Figure 66. Schematic view of (4,6)-connected gek2 net. existence of a similar phenomenon in coordination polymers,
which are distinct from polymorphism.447 Supramolecular
DCPPT as a 3-connected node to produce this 2D MOF with isomerism is the existence of more than one type of network
a (3,10) connected net of vertex type [(3 2 .4) 2 - structures for the same molecular repeating unit. Nowadays,
(38.414.512.611)].432 This unprecedented 2D net can be supramolecular isomerism encompasses a variety of different
considered as being composed of a (3,6)-connected CdCl2 types of structural and stereo isomerism in CPs and
net formed by the repeating unit and the triply bridging
MOFs.448−450 Here, we discuss the supramolecular isomerism
DCPPT and a (4,4) net constructed by double bridges (Figure
in 2D MOFs below.
67).
For a CP with the chemical composition of ML1.5,
honeycomb, brick wall, herringbone, fes, and bilayer structures
are the possible supramolecular isomers in 2D MOFs (Figure
68). The 1D CP, ladder or railroad structure (Figure 68a), and
a 3D MOF (Figure 68g) are also supramolecular isomers as
they have the same chemical formula but different structures.
Although all of these are the possible supramolecular
isomeric structures, in reality, there is no single material with
the same chemical formula exhibits more than one supra-
molecular structure reported. This is probably due to the
kinetics of crystallization, which favors one isomer predom-
Figure 67. (a) Chemical structure of DCPPT ligand and (b) view of inantly. For example, the 1D CP [Ag(pyrimidine)][BF4]·H2O
one of the [Co 8 N 2 (μ 3 -OH) 4 (CO 2 ) 1 2 (H 2 O) 4 ] SBUs in with M:L stoichiometry of 1:1 has a brick wall structure due to
[Co8(DCPPT)6(μ3-OH)4(H2O)4]·5H2O. Adapted with permission Ag···Ag interactions (3.190 Å). The planar packing of the
from ref 432. Copyright 2007 American Chemical Society. adjacent 1D chains are responsible for the formation of this
structure.320,451 When the spacer ligand is changed to bpy, the
A rare (3,12)-connected 2D network [Zn 8 (trz) 4 - adjacent linear 1D CPs are packed in perpendicular direction
(OH)4(pa)4] (H2pa = 1,2-benzenedicarboxylic acid; (Htrz = to furnish a 3D structure in [Ag(bpy)](NO3).452,453

Figure 68. Supramolecular isomerism for ML1.5. (a) Ladder, (b) honeycomb, (c) brick wall, (d) herringbone, (e) fes, (f) bilayer, and (g) 3D MOF.

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In another example, [M2(tpt)2(btec)] (M = Zn and Cu), generated arising from the orientations of the phenylene rings
Zn(II), and Cu(II) exhibit two different bilayer structures, but above and below the square planes (sql-1 and sql-2).369 The
they have the same ML ratio with the same ligands (see section third supramolecular isomer, sql-3 has been observed in
2.3.8). These highlight the subtle influence of metal ions on [In(1,3-bdc)(1,3-Hbdc)]·2DMF. The tetrahedral In(III) cen-
the formation of two different bilayer structures.414 Further, ter is bonded to three chelating carboxylates and one
Kitagawa et al. have shown that for the same ML ratio in carboxylic acid. The orientation of the phenylene ring around
[M2(azpy)3(NO3)4], Co(II) furnished a brick wall structure, the square plane is distinctly different from the other two
while Cd(II) provided the herringbone isomer as discussed in isomers.60,455
section 2.3.3.2 and 2.3.3.3.126 A dicarboxylate spacer ligand such as 1,4-bdc can be bonded
For the chemical formula ML2, a few supramolecular to the metal ions in three different ways utilizing their chelating
isomers in 1D CP, 2D and 3D MOFs are shown in Figure 69. and bridging nature (Figure 71a). These bonding modes in sql
lattices can generate two structural isomers as shown in Figure
71b,c. The isomer containing both type-I and type-II
dicarboxylate bonding (Figure 71b) has an ideal rectangular
shape with mm symmetry. The second isomer with type-III
linkage has the shape of an ideal square with 4-fold rotational
symmetry (Figure 71c). These theoretically possible isomers
have never been synthesized or isolated in 2D MOFs.
However, these connectivity have been found in the pillar-
layered MOFs.456 In another case, they have been reported in
two different pillar-layered MOFs.457,458

3. DIFFERENT ENTANGLEMENTS
Figure 69. Supramolecular isomers for M:L ratio of 1:2: (a) chain, A rich variety of distinct structural types has been documented
(b) ribbon, (c) sql net, (d) kgm net, and (e) dia 3D net. in the literature, which have constantly enriched our
knowledge in the field of MOFs. Like nature, crystals also
Bharadwaj et al. synthesized a 1D chain CP from a 2D MOF despise vacuum and as a result led to the generation of
with sql topology in an SCSC manner (see section 4). When different entanglements to accommodate space, which have
the single crystals of the non-interpenetrating 2D MOF with been extensively studied by different prominent groups. An
(4,4) topology was soaked in 0.1% formaldehyde in chloro- entangled system can be defined as an extended periodic array
form solution for 5 days, its supramolecular isomer was of similar or different individual motifs formed via interweaving
isolated.454 or interlocking. These include (i) interpenetration, (ii)
For the sql net, an angular dicarboxylate ligand generates polycatenation, (iii) polyrotaxane, and (iv) interdigitation.
three different supramolecular isomers (Figure 70). When the Initially, most common type entanglement investigated was
angular spacer ligand 1,3-benzenedicarboxylate (1,3-bdc) was interpenetration and later on with more designable ligands,
used to synthesize 2D MOFs [M2(1,3-bdc)2(py)4], (M = Zn increase in complexity of the flexible structures are observed
and Cu), two different supramolecular isomers in sql net were that led to the discovery of other interlocked systems. A wide
range of excellent review articles have been marked by Robson,
Batten, Ciani, Carlucci, Blatov, Zhou, Lu, Maji, and other
groups in which they have rationalized these systems more
elaborately.46,56,72,459−465 These are treasures for those work-
ing in this area and therefore, in this review, we focus on 2D
MOFs with a view to understand the design and construction
of different types of coordination polymeric sheets.
3.1. Interpenetrated and Polycatenated Structures
Interpenetration and polycatenation are two closely related
terminologies in entanglements of MOFs mostly with flexible
architectures. However, there are some varied features as
exemplified by the groups of Robson, Batten, and
Ciani72,459,460 and followed by Zhou, Carlucci, and Bla-
tov,46,462 which make the definition of these two systems
distinctive. Accordingly, in the case of interpenetration, a finite
number of individual motifs usually of identical topology
(extended 2D or 3D nets) are involved with each motif
interlacing with others to result into an infinite extended array
with same dimensionality. As a contrary, polycatenation means
Figure 70. Schematic representing three possible types of sql layer
a finite or infinite number of similar or different type motifs
types obtained with isophthalate and square paddlewheel MBBs (sql- (0D or 1D or 2D with closed circuits) entangle to result in a
1 and sql-2) or isophthalate and tetrahedral indium MBBs (sql-3). higher dimensional structure in which each motif interlaces
Orange lines represent isophthalates pointing “up”, while blue lines only with the neighboring motifs and not with all. Because
represent isophthalates pointing “down”. Reproduced with permission most of the interpenetration or polycatenation based aspects
from ref 60. Copyright 2014 Royal Society of Chemistry. until 2014 are elaborated in a detailed manner in the previously
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Figure 71. (a) Three types of connectivity of 1,4-bdc from the chelating and bridging modes. Two structural isomers in the double-pillared layer
structure [M2(dicarboxylate)2(pillar)2]. (b) The (4,4) “rectangular” net has an idealized local mm symmetry with type-I and type-II linkages. (c)
The (4,4) “square” net has an idealized local 4-fold rotational symmetry with type-III connectivity of dicarboxylates. Rhombus shape is also possible
for type-III linkage. The axial positions are occupied by dipyridyl pillar ligands, which are not shown for clarity. Reproduced with permission from
ref 456. Copyright 2019 International Union of Crystallography.

mentioned reviews, we will selectively mention some well-

known early reported examples followed by the newly reported
structures. In this subsection, we will discuss those with similar
dimensional networks, i.e., (i) 1D to 2D, (ii) 2D to 2D, and
(iii) 2D to 3D. The definitions mentioned above clearly clarify
that 2D to 2D entangled structures fall under interpenetration,
whereas 1D to 2D and 2D to 3D structures are typically
polycatenated structures. These can further be classified as
parallel and inclined modes depending upon the mode of
orientation and interrelation between individual motifs. In this
subsection, we will illustrate these categories in a compact way.
3.1.1. 1D to 2D Structures. The simplest 1D CPs may Figure 72. (a) Schematic representation of warp-and-woof type sheet.
assist in the construction of 2D layer due to (i) interweaving Structures of (b) [Cu(2,2′-bpy)(azpy)(H2O)](NO3)2·H2O, (c)
(warp and woof), (ii) fence (chicken) wiring, (iii) parallel or [HgI2(bpmbpt)], (d) [Mn(salen)Au(CN)2]4(H2O), (e) [Mn-
inclined polycatenation of ladder, tube and ribbon-like chains, (acacen)Ag(CN)2], and (f) [Pb(bpe)(CH3COO)(CF3COO)]. (a)
or (iv) entanglement by rotaxane-type structures.466,467 Here, Reproduced with permission from ref 80. Copyright 2011 Royal
we will discuss the first three possibilities, and the last option Society of Chemistry. (b) Adapted with permission from ref 468.
will be elaborated in section 3.3.1.1. Copyright 2000 Royal Society of Chemistry. (c) Reproduced with
3.1.1.1. Interweaving of 1D Chains. The first example with permission from ref 469. Copyright 2003 Royal Society of Chemistry.
(d,e) Reproduced with permission from ref 470. Copyright 2007
warp-and-woof type interwoven 1D zigzag chains to form 1O/ Royal Society of Chemistry. (f) Adapted with permission from ref
1U (one over and one under) 2D entangled structure has been 473. Copyright 2008 American Chemical Society.
discovered by Ciani and co-workers in 1D CP [Cu(2,2′-
bpy)(azpy)(H2O)](NO3)2·H2O.468 The schematic representa-
tion of warp-and-woof sheet is shown in Figure 72a. In this, the (bpmbpt = 2,6-bis(4-pyridinylmethyl)benzo[1,2-c:4,5-c′]-
corners formed by Cu(2,2′-bpy)2+ units are connected via cis- dipyrrole-1,3,5,7(2H,6H)-tetrone) was reported by zur Loye
coordinated azpy spacers and two such chains propagate in two and co-workers with the zigzag chains propagating in
different directions (Figure 72b). Another interesting example perpendicular directions (Figure 72c).469 Similarly, [Mn-
based on 2O/2U interwoven 2D structure, [HgI2(bpmbpt)] (salen)Au(CN) 2 ] 4 (H 2 O) (salen = N,N′-ethylene-bis-
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(salicylideneaminato), [Mn(acacen)Ag(CN)2] (acacen = Scheme 1. Schematic Views of 1D to 2D Polycatenation by

N,N′-ethylene-bis(acetylacetonylideneiminate)) and [Zn- (a) Step-ladders in Parallel Fashion, (b) Normal Ladders,
(bac)2(bpp)]·1.5H2O (bac = 1-benzoylacetone) display (c) Ribbons in Inclined Fashion, and (d) Tubes Yielding in
identical warp-and-woof type cloth-like array formed by two Parallel Fashion
almost orthogonal 1D helical chains with different chirality
(Figure 72d,e).470,471 Later, LaDuca et al. also reported an
identical 1D CP [Cu(ox)(dpa)(H2O)] (ox = oxalate; dpa =
4,4′-dipyridylamine).472 Complex [Pb(bpe)(CH 3COO)-
(CF3COO)] with 1D spiral chains also features similar
structure in which the chains are almost parallel, however,
perpendicular with respect to CC bond (Figure 72f).473
3.1.1.2. Fence or Chicken Wiring of 1D chains. Earlier, an
inorganic compound achiral NaAuS reported by Kanatzidis et
al. exhibit chicken-wire like array with AuS− mesohelical chains
entangled in a parallel manner (Figure 73a).474 Later, Zhang

Figure 73. (a) Schematic view of the chicken-wire network. (b)

Space-filling representation of chicken-wire mesh in [Ag(ipim)].
Adapted with permission from ref 80. Copyright 2011 Royal Society
of Chemistry.

and co-workers have reported a chicken-wire fencing in

[Ag(ipim)] (ipim = isopropylimidazolate).80 This comprises
four flattered arc-joints linked to two types of fragments. The
first two link to three adjoining arcs to a flat (DA 8.5 and 4.01),
S-shaped fragment, whereas the remaining two connect three
neighboring arcs to a spatial (DA 23.9 and 21.51) (DA = Figure 74. (a) 1D helical channel chain without parallel catenation in
dihedral angle), helical fragment. These S-shaped and helical [Ni(OBA)(L1)]·H2O. A schematic view of 1D to 2D parallel
polycatenated framework in (b) [Ni(OBA)(L1)]·H2O and (c)
fragments interlink alternately to build an intricate helix with a
2C4H8O2@[Ag(PF6)L. (a,b) Adapted with permission from ref 477.
very long helical pitch of 63.8 Å through hydrophobic Copyright 2013 Royal Society of Chemistry. (c) Reproduced with
interactions and construct a homochiral chicken-wire mesh permission from ref 478. Copyright 2020 American Chemical Society.
(Figure 73b).
3.1.1.3. Parallel or Inclined Polycatenation of 1D Chains.
Construction of 2D architectures can also be achieved from the (H2O)]·8.2H2O (IIMB = 1-(1-imidazolyl)-4-(imidazol-1-
1D step-ladder, ribbon-like, or tubular CPs in a parallel or ylmethyl)benzene) with ribbon-like double-stranded chains
inclined fashion (Scheme 1). display inclined 1D to 2D polycatenation (Scheme 1c).480,481
The well-known examples for parallel polycatenated 1D to The 1D CPs, [Zn(H2pbta)(bibm)]·H2O (H4pbta = 5,5′-
2D structures are [Cu2L3(MeCN)2]X2·solvent (L = 1,4-bis(4- phenylenebis(methylene)-1,1′-3,3′-(benzene-tetracarboxylic
pyridyl)butadiene and X = PF6−, BF4−) reported by Schröder acid; bibm = 4,4′-di(1H-imidazol-1-yl)-1,1′-biphenyl), exhibit
et al. [Cu2L3(MeCN)2](PF6)2 consists of undulated 1D rectangle-shaped nanotube-like 1D polymers with parallel
ladders with tetrahedral Cu(I) centers, and each ladder is polycatenation (Scheme 1d).482 A later study by Turner et
polycatenated to four neighboring ladders (Scheme 1a).475 al. revealed a chiral 1D CP [Cd(AlaNDI)(DMF)2] based on
Two isostructural 1D CPs, [M(OBA)(L1)]·xH2O [M = Ni, NDI-metallomacrocycles with similar polycatenation of 1D
Cd; x = 1, 2] (H2OBA = 4,4′-oxybis(benzoic acid); L1 = ), loop-like chains.483
with helical channels also show parallel polycatenation (Figure 3.1.2. 2D to 2D Structures. The entanglement of same
74a,b).476,477 A recent example based on 1D zigzag ladders, types of 2D nets in a parallel manner for the construction of
2C 4 H 8 O 2 @[Ag(PF 6 )L] (L = benzene-1,3,5-triyltris- overall 2D interpenetrated framework has been observed in a
(methylene))tris(oxy))tris(benzene-4,1-diyl))tris(methylene)- wide variety of 2D MOFs. The main requirement for this
triisonicotinate), has been reported by Jung et al. (Figure interpenetration to occur is corrugation of 2D sheets. A typical
74c).478 On the other hand, inclined polycatenation is noted in example of this type is [Ag(tcm)] (tcm = tricyanomethanide)
the ladder-like 1D polymers in [Cd(bpmb)1.5](NO3)2, [Cd- based on corrugated 2D 63 nets investigated by Britton,
(bpmb)1.5](NO3)2·C6H4Br2, and [Cu2(ip)(bpy)]·3.5H2O (ip Robson, and Batten’s groups. The interpenetration takes place
= isophthalate) (Scheme 1b). 320,479 Similarly, [Cu- in between the peaks and troughs of adjacent sheets which lie
(IIMB)2(SO4)]·8.5H2O, [Co(IIMB)2(H2O)(SO4)]4·29H2O, above and below relative to each other.270,484,485 Interestingly,
[Cd(IIMB)2(H2O)(SO4)]·7.5H2O, and [Mn(IIMB)2(SO4)- parallel interpenetration in [Ag(TEB)(CF3SO3)] (TEB =
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1,3,5-tris(4-ethynylbenzonitrile)benzene) led to 6-fold inter- [Re4(CO)12(OH)4]·2bpy·2MeOH shows mode C type inter-

penetration in undulating hexagonal layers (Figure 75).486 penetration.490
Apart from these, another interesting way of 2D to 2D
interpenetration involves Borromean links with three nets,
which make two non-interpenetrating nets entangle in the
presence of a third net. A unique example of this case is
[Cu2(tmeda)2{Au(CN)2}3](ClO4) (tmeda = N,N,N′,N′′-
tetramethylethylendiamine) made up of wavy 63 sheets with
Cu(tmeda)2+ units as nodes which are connected to linear
chains of Au(CN)2− units (Figure 77).491 More examples of
this type have been discussed in the literature.56,72,460,463

Figure 75. Six-fold 2D → 2D parallel interpenetration in [Ag(TEB)-

(CF3SO3)]. (a) A single layer and (b) a view of the interpenetrated
structure. Figure 77. (a) Borromean interpenetration of rings. (b) 2D → 2D
parallel interpenetrating sheets in [Cu2(tmeda)2{Au(CN)2}3](ClO4).
Adapted with permission from ref 56. Copyright 2014 John Wiley &
Another classic example has been reported by Champness and Sons.
co-workers in [Cd2(NO3)4(dpt)2(MeCN)] (dpt = 2,4-bis(4-
pyridyl)-1,3,5-triazine; bent dipyridyl ligand) with fes topology Some recent examples featuring 2D to 2D parallel
net (4.82).487 interpenetration are illustrated here. Arici reported an
The (4,4)-connected nets can also exhibit parallel inter- undulated 2D MOF, [Zn(μ-HCIP)(μ-1,4-bix)]·2H 2 O
penetration in four topologically different modes like (6,3)- (H3CIP = 5-(4-carboxybenzylamino)isophthalic acid; 1,4-bix
connected nets as illustrated by Batten and Robson (Figure = 1,4-bis(imidazole-1ylmethyl)benzene), with sql topology
76).56,72 The 2D MOF [Cu(tcm)(bpy)] with corrugated sheet based on a flexible bidentate bridging ligand H3CIP connected
show parallel interpenetration of mode A, while [Cd(4- to distorted tetrahedral Zn(II) centers.492 It displays 2-fold
pic)2(Ag(CN)2)2](4-pic) (4-pic = 4-methylpyridine)exhibit interpenetration and also show interdigitation (see section 3.4)
interpenetration of mode B in which troughs of one sheet are due to presence of partly deprotonated HCIP ligand. Other
relatively offset with respect to peaks of another sheet.488,489 similar MOFs showing only 2D to 2D parallel interpenetration
On the other hand, hydrogen bonded complex are found in [Cd(btrb)(ip)(H2O)]·H2O (btrb = 1,4-bis(1,2,4-
triazol-4-ylmethyl)benzene) and [Co(diimpym)(npta)·
CH3OH] (diimpym = 4,6-di(1H-imidazol-1-yl)pyrimidine;
H2npta = 5-nitroisophthalic acid).493,494 Two identical
corrugated (4,4)-connected 2D layers [Zn(L)(oba)]·H2O
and [Co(L)(oba)]·H2O exhibit 3-fold interpenetrated struc-
ture containing an interlaced triple-stranded helix.495 Three
identical helical chains with the same chirality entangle with
the triple-stranded helix of opposite chirality from the
adjoining layers. Another 2D sql MOF [Cd(m-pdoa)(bpp)-
(H2O)]·2H2O] (m-H2pdoa = 1,3-phenylenedioxy diacetic
acid) with unusual homochiral bilayers also display similar
interpenetration.496 Similarly, [Mn(NCS)2L2] (L = bis(4-
pyridyl) substituted hydrazone derivatives) with triply inter-
penetrating corrugated 2D sheets are reported by Batten and
co-workers.497
Nagaraja et al. also reported two 2D MOFs with sql net,
[Zn 2 (muco) 2 (azopy) 2 ]·3DMF·2H 2 O and [Cd(muco)-
(4bpdh)(H2O)], based on trans,trans-muconate dianion
(muco) and different linkers 4,4′-bisazobipyridine (azopy)
and 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (4bpdh), re-
spectively.498,499 The former one exhibits 2-fold interpenetra-
tion, while the latter displays 3-fold interpenetration (Figure
Figure 76. Four different interpenetration topologies for pairs of (4,4) 78). Several other 2D MOFs of this type are reported in the
sheets: (a) mode A, (b) mode B, (c) mode C, and (d) mode D. recent literature.311,500−515
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Figure 78. (a,b) 2-Fold interpenetration in [Zn2(muco)2(azopy)2]·

3DMF·2H2O and (c−e) 3-fold interpenetration in [Cd(muco)-
(4bpdh)(H2O)]. (a,b) Adapted with permission from ref 498.
Copyright 2014 Royal Chemical Society. (c−e) Adapted with
permission from ref 499. Copyright 2016 Royal Chemical Society. Figure 80. 2D to 3D polycatenation in (a) [Ag2L3]X2 with
Borromean layers and (b,c) [Cd(in) 2 (bpee) 1/2 (H 2 O)] and
3.1.3. 2D to 3D Structures. The dimensional increment in [Cu4(dca)4(bpy)3(MeCN)2] with thick bilayers, respectively. (a)
2D MOFs to 3D frameworks can be envisaged in two ways: (i) Adapted with permission from ref 56. Copyright 2014 John Wiley &
Sons. (b) Reproduced with permission from ref 46. Copyright 2014
parallel polycatenation in which parallel mean planes are
American Chemical Society. (c) Reproduced with permission from ref
present and (ii) inclined polycatenation in which unparalleled 56. Copyright 2014 John Wiley & Sons.
mean planes crisscross at an angle. These different modes are
explained below.
3.1.3.1. Parallel Polycatenation. When the degree of isonicotinate) and [Cu4(dca)4(bpy) 3(MeCN)2] (dca =
corrugation is extreme or thick 2D nets such as bilayers or dicyanamide) with offset parallel bilayers containing four and
other identical nets are present, then 2D to 3D parallel six membered motifs, respectively, represent this type of
polycatenation takes place. A typical example of 2D to 3D catenation (Figures 80b,c).519,520
parallel polycatenation in undulating 2D layers is [Cu- Few other 2D MOFs based on undulating sheets and
(bpe)1.5(PPh3)](PF6)·1.5DCM consisting of puckered hexag- bilayers to display 2D to 3D parallel polycatenation are also
onal motifs with chair conformation and two layers are reported recently. Harrowfield et al. reported a chiral 2D MOF
catenated in “above and below” manner (Figure 79a).516 [(UO2)2K2(C7)3(H2O)]·0.5H2O with 82.10 (kla) net topology
based on a α,ω-dicarboxylic acid (C7 = (HOOC-(CH2)5-
COOH)) showing parallel polycatenation between convoluted
layers (Figure 81a,b).521 Very recently, Deng and co-workers
illustrated a Borromean type 2D to 3D polycatenation in
[Zn(3-PBI)(H2O)] with hcb net topology and derived from a
semirigid ligand 5-(4-pyridin-3-yl-benzoylamino)isophthalic
acid (3-H2PBI) (Figure 81c).223 Other similar wavy 2D
structures of this kind have been reported.522−527

Figure 79. (a) 2D to 3D polycatenated structures with undulating

layers in [Cu(bpe)1.5(PPh3)](PF6)·1.5DCM. (b,c) Single and inter-
penetrated structures of [Cu3(bpy)2(pydc)2]·4H2O, respectively. (a)
Adapted with permission from ref 46. Copyright 2014 American
Chemical Society.

Another remarkable example is [CuI2CuII(bpy)2(pydc)2]·

4H2O (pydc = pyridine-2,4-dicarboxylate) involving two sets
of hexagonal layers in which each set is composed of non-
catenated parallel layers, but both sets get entangled as offset
dispositioned waves (Figure 79b,c).517
Like 2D to 2D parallel interpenetration, Borromean layers
are also observed for 2D to 3D parallel polycatenation. An
Figure 81. (a) View of the topological connectivity of the uranyl-
example of this case is [Ag2L3]X2 (L = N,N′-bis(salicylidene)- based 2D subunit in [(UO2)2K2(C7)3(H2O)]·0.5H2O (yellow,
1,4-diaminobutane; X = NO3, ClO4) also containing (6,3)- uranium; blue, centroid of dicarboxylate ligand). (b) Four of the
connected puckered sheets with 3-connecting Ag(I) metal polycatenated 2D arrays viewed edge-on. (c) 2D to 3D polycatena-
centers (Figure 80a).518 A set of bilayers based 2D tion in [Zn(3-PBI)(H2O)]. (a,b) Adapted with permission from ref
coordination networks arranged in parallel exhibits 3D 521. Copyright 2019 American Chemical Society. (c) Adapted with
polycatenation. For example, [Cd(in)2(bpee)1/2(H2O)] (in = permission from ref 223. Copyright 2019 American Chemical Society.

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Two pillared-bilayer 2D frameworks, [Cd(fdc)(bpy)1.5] and as rods from another sheet. In diagonal/diagonal mode, the
[Cd2(fdc)2(4-bpdb)3]·1.5(4-bpdb)·2H2O (fdc = 2,5-furandi- windows of each sheet contain the nodes from the other
carboxylate; 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-buta- catenating sheets. In parallel/diagonal modes, two different
diene) with {48.62} net topology and thickness of 11.77 and sets of sheets (A and B) are present: the windows of set A
15.96 Å, respectively, have been reported (Figure 82a,b).528 accommodate the rods of set B, while the windows of set B
accommodate the nodes of set A. Robson and Batten’s group
also investigated this in details as well.72,459
One of the earliest reports of this category is described by
Zaworotko and co-workers in the (6,3)-connected 2D Cu(I)
based sheet [Cu2(pz)3](SiF6) with parallel/parallel mode of
inclination (Figure 83a). 534 Another example is [M-

Figure 82. 2D to 3D polycatenated structures of (a) [Cd(fdc)(4,4′-

bpy)1.5], (b) [{Cd2(fdc)2(4-bpdb)3}·1.5(4-bpdb)·2(H2O)], (c) Figure 83. Inclined polycatenation with (a) parallel/parallel and (b)
(Et2NH2)2[K2Zn4(TPA)4(DBO)2]·8(EtOH)·15(DEF), and (d) [Cd- diagonal/diagonal modes. (a) Reproduced with permission from ref
(L)(bpy)]·DMF·H2O. (a,b) Adapted with permission from ref 528. 460. Copyright 2003 Elsevier. (b) Reproduced with permission from
Copyright 2015 American Chemical Society. (c) Adapted with ref 56. Copyright 2014 John Wiley & Sons.
permission from ref 529. Copyright 2017 Royal Society of Chemistry.
(d) Adapted with permission from ref 530. Copyright 2018 Royal
Society of Chemistry.
(bpy)2(H2O)2](SiF6) (M = Zn, Cu, Cd) containing (4,4)
polycatenated layers with the diagonal/diagonal orientation
On the basis of a nanosized tritopic ligand tris(4′- reported by Robson et al. (Figure 83b).107 Similarly, Plater et
carboxybiphenyl)amine (TPA), an unusual tetra layered 2D al. reported two unique examples: [Cd(NO3)2(L)2] (L = 1,6-
MOF (Et2NH2)2[K2Zn4(TPA)4(DBO)2]·8(EtOH)·15(DEF) bis(4-pyridyl)hexane) with (4,4) layers exhibit diagonal/
was investigated by Zhang et al., exhibiting a rare (3,4,8)- diagonal mode of catenation, whereas [Cd(SO4)(bpp)3]
connected topology (Figure 82c).529 On a similar note, Wang containing both four and six-membered polygons show
and co-workers reported two identical MOFs [Cd(L)(bpy)]· unusual entanglement in which hexagonal windows are
DMF·H2O and [Cd2(L)2(bpe)2]·3DMF·2.5H2O (H2L = 4,4′- catenated by four and square windows by two inclined
[benzene-1,3-diylbis(methanediylsulfanediyl)] dibenzoic acid) sheets.535 This can be regarded as a parallel/diagonal mode of
with a layer-type 3-fold 2D to 3D polycatenation (Figure inclination.
82d).530 Other related MOFs with bilayer polycatenation are Some unique cases are also observed in this category. The
[Cd(m-pda)(o-bib)]·H2O (H2pda = phenylenediacetic acid; 2D MOF [Ni(azpy)2(NO3)2]2[Ni2(azpy)3(NO3)4]·4DCM
bib = 1,4-bis(imidazol-1-ylmethyl)benzene), [Zn(bbib)(ip)] consists of two different types of 2D layers, one based on
(bbib = 1,3-bis(benzimidazolyl)benzene), and [Cd- (4,4)-connected square grid and the other with (6,3)-
(DIA)1.5(cdc)] (DIA = 9,10-di(1H-imidazol-1-yl)anthracene; connected brick wall hexagonal grids in a ratio 2:1.127 These
H2cdc = 4,4′-carbonyldibenzoic acid).527,531,532 two layers display inclined catenation at an angle of 45°, with
3.1.3.2. Inclined Polycatenation. Zaworotko et al. thor- each square of the former sheet entangled by a single layer of
oughly investigated different topological modes in inclined the latter type and each rectangular window of the brick wall
polycatenation of (4,4)-connected nets.448,533 This can be layers catenated by two square grids (Figure 84a). Another
classified into three categories based on their orientation and notable example is [Co2(azpy)3(NO3)4]·Me2CO·3H2O based
way of catenation: (a) parallel/parallel, (b) diagonal/diagonal, on four different set of (6,3) brick wall type sheets.
and (c) parallel/diagonal (Scheme 2). In parallel/parallel Interestingly, every hexagonal windows of a layer are
mode, windows of one sheet are catenated by the sides acting interlocked by three other nets, each belonging to rest of the
other distinct sets (Figure 84b). 126 The 2D MOF
Scheme 2. Different Modes of Inclined Polycatenation: (a) [Ni6(bpee)10(H2O)16](SO4)6·xH2O is also found to comprise
Parallel/Parallel, (b) Diagonal/Diagonal, and (c) Parallel/ three different sets of (4,4) layers exhibiting mutual inclined
Diagonal polycatenation along three different spatial orientations
(Figure 84c).536 An exceptional example reported by Moore
et al. is [AgL2](SbF6) (L = 3-cyanophenyl-4-cyanobenzoate).
It is based on (4,4)-connected 2D wavy layers which exhibit
coexistence of both two-fold parallel interpenetration within
one set of layers and diagonal/diagonal type inclined
polycatenation between two differently oriented sets, resulting
in the formation of a 3D structure (Figure 84d).537
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parallel/diagonal mode of inclined polycatenation between two

similar sets of parallel sql sheets and capable as an efficient
hydrogen storage material.541 Several other relevant examples
are provided in the literature.215,502,524,542−549
3.2. 2D MOFs with Mixed Dimensional Frameworks
In addition to the aforementioned frameworks, those involving
2D MOFs with different dimensional networks like 1D or 3D
are discussed here.
3.2.1. 1D + 2D to 2D or 3D Structures. Morsali et al.
described the first rare case of 1D + 2D to 2D parallel
polycatenated array in [Hg2(μ-4bpdh)(μ-SCN)4][Hg2(μ-
Figure 84. Different unique examples of inclined polycatenation in
4bpdh)(μ-SCN)4]2 with 1D ladders made up of thiocyanate-
(a) [Ni(azpy) 2 (NO 3 ) 2 ] 2 [Ni 2 (azpy) 3 (NO 3 ) 4 ]·4DCM, (b) bridged {Hg2(SCN)4} nodes and 4bpdh rods which interlock
[Co2(azpy)3(NO3)4]·Me2CO·3H2O, (c) [Ni6(bpee)10(H2O)16]- inside the hexagonal 2D net (Figure 86).550
(SO4)6·xH2O, and (d) [AgL2](SbF6) with both parallel inter-
penetration (left) and inclined interlocking (right). (a) Reproduced
with permission from ref 460. Copyright 2003 Elsevier. (b)
Reproduced with permission from ref 56. Copyright 2014 John
Wiley & Sons. (c) Adapted with permission from ref 536. Copyright
2003 Royal Society of Chemistry. (d) Reproduced with permission
from ref 460. Copyright 2003 Elsevier.

Chen et al. reported two different types of (4,4) nets Figure 86. Schematic representation of 1D + 2D = 2D parallel
interpenetrating in parallel/diagonal inclined fashion to furnish polycatenation. Reproduced with permission from ref 550. Copyright
a 3D material that shows spin canting and metamagnetism. In 2009 Royal Society of Chemistry.
the compound [Co4(pico)4(bpy)3(H2O)2]·2H2O (pico = 3-
hydroxypicolinate), the first corrugated sheet has two distinct Ciani and co-workers synthesized a remarkable 1D + 2D to
Co(II) atoms. One distorted octahedral Co(II) atom 3D inclined polycatenated framework [Cu5(bpp)8(SO4)4-
coordinated by two O,N-chelating pico ligands and two bpy (EtOH)(H2O)5](SO4)·EtOH·25.5H2O, which involves rib-
ligands, while the second Co(II) atom is coordinated by two bon-like 1D rings and 2D (4,4)-connected tessellated sheet. An
O,O′-chelating pico ligands and two bpy ligands. The second individual square in 2D layer is catenated by two rings from
(4,4) net is made up of [Co2(pico)2(bpy)(H2O)2] in which different ribbons as well as each ring is interlocked by two
the [Co2(pico)2(H2O)2] chains are interlinked through bpy adjoining layers (Figure 87).551 Ciani’s group also reported
ligands (Figure 85).538

Figure 85. Two different types of (4,4) sheets present in

[Co4(pico)4(bpy)3(H2O)2]·2H2O. Adapted with permission from
ref 538. Copyright 2005 John Wiley and Sons.

In recent times, several other structures with this type of

polycatenation are also documented in the literature. Figure 87. Inclined polycatenation between 1D ribbons and (4,4)-
Zaworotko et al. reported two remarkable examples of mixed connected 2D sheets in [Cu5(bpp)8(SO4)4(EtOH)(H2O)5](SO4)·
EtOH·25.5H2O. Reproduced with permission from ref 551. Copy-
parallel-inclined polycatenation in identical sql net, [M- right 2000 John Wiley & Sons.
(L) 2 (NO 3 ) 2 ]·H 2 O (M = Co, Ni) (L = N,N′-(1,4-
phenylenebis(methan-1-yl-1-ylidene))bis(4-(1H-imidazol-1-
yl)aniline)).539 Similar to one reported by Moore et al., these another MOF [Mn2(1,4-bix)3(NO3)4]·2CHCl3 in their later
two also possess 2-fold parallel interpenetration and inclined study, which involves 1D ladder instead of ribbons and 2D
polycatenation within the same framework to afford an overall brick wall layers to generate a similar polycatenated array.552
4-fold 3D polycatenated architecture. Sinha and co-workers Other relevant examples of this type are [Cd3(bbtz)6(H2O)6]-
reported two isostructural MOFs [Zn(INH)(succ)] and (BF4)6·1.75H2O (bbtz = 1,4-bis(1,2,4-triazol-1-ylmethyl)-
[Zn(INH)(fum)] (INH = isoniazid; succ = succinate; fum = benzene) and [Ni3(H2O)6(bpy)4(SIPA)2]·8H2O (H3SIPA =
fumarate) with (4,4)-connected sql net undulating sheets and 5-sulfoisophthalic acid) involving 1D ribbons/undulating 2D
exhibit inclined parallel/parallel intercatenation.540 Ghoshal et layers and 1D chains/2D bilayer motifs, respectively.553,554
al. investigated a dynamic 2D MOF [Cu(bpee)(2-ntp)- 3.2.2. 2D + 3D to 3D Structures. Very few examples are
(H2O)2]·2H2O (2-ntp2− = 2-nitroterephthalate), which display reported in the literature with 2D and 3D nets hetero-
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combinations to form 3D polycatenated structures. Zhang et al. chains fall under trivial entanglements. In this category, four
reported an interesting MOF [(CH3)2NH2][Zn2(1,4-bdc)- types of modes are involved as shown in Figure 89. In mode
(BTB)]·3DMF·2H2O (BTB = 4,4′,4″-benzene-2,4,6-triyltri-
benzoate) constructed from 2D (6,3) bilayer and unprece-
dented (3,5)-connected 3D hexagonal mesoporous silica
(hms) net. Each 2D bilayer is parallelly catenated in between
the sheets of the 3D framework (Figure 88a).555 Another rare

Figure 89. Different modes of 1D to 2D polyrotaxane MOFs: (a)

mode IA, (b) mode IB, (c) mode IC, and (d) mode ID. Adapted with
Figure 88. (a) Schematic view of 2D 63 and 3D hms net. Adapted permission from ref 559. Copyright 2012 Royal Society of Chemistry.
with permission from ref 555. Copyright 2009 American Chemical
Society. (b) Network perspective of the interpenetrated array of 2D IA, loops and rods from individual 1D chains intersect in an
(4,4)-connected +3D pcu nets. Reproduced with permission from ref inclined fashion to generate 2D polyrotaxane MOFs (Figure
556. Copyright 2011 Royal Society of Chemistry. 89a). The first example in mode IA, [Ag2(1,4-bix)3]·(NO3)2
was investigated by Robson et al., which is composed of
example is [Co(1,4-bdc)(dia)(H2O)·Co(1,4-bdc)(dia)2·H2O] macrocyclic loops formed by two Ag(I) atoms and two 1,4-bix
(dia = 9,10-di(1H-imidazol-1-yl)anthracene) featuring a 3D ligands and further interlinked by another 1,4-bix serving as a
pcu net polycatenated by 2D (4,4)-connected layers in an rod (Figure 90a).561 A few other examples associated with this
inclined fashion (Figure 88b).556 Chung and co-workers also
reported a similar network [{[Co(mppe)2(NCS)2]·2[Co-
(mppe)2(NCS)2]}·5CH3OH] (mppe = 1-methyl-1A-(4-pyr-
idyl)-2-(4-pyrimidyl)ethylene).557
3.3. Polyrotaxane Structures
Polyrotaxanes can be defined as a type of entanglement with
extended polythreaded systems containing periodic arrays of
molecular rotaxanes, which can be or cannot be disentangled
without separating internal linkages. On the other hand, Figure 90. View of 1D to 2D inclined (a) polyrotaxane and (b)
polypseudorotaxanes have also been observed arising from the armed polyrotaxane MOFs. Adapted with permission from ref 559.
extended arrangements of the pseudo-rotaxanes that can be Copyright 2012 Royal Society of Chemistry.
slipped off into disentangled motifs. On the basis of the
separation factor, this type of systems is classified as trivial and
nontrivial entanglements in which the trivial ones can be type include [Cu2(bpf)3(NO3)2] and [Ag2(bpf)3(NO3)2] (bpf
separated without breaking connections and nontrivial ones = 1,4-bis(4-pyridylmethyl)-2,3,5,6-tetrafluorobenzene),562
with infinite structural motifs containing capping stoppers [Cd2(1,4-bix)3(SO4)2],563 [Ca2{H2(p-CO2)TPP}(H2O)8]·py
cannot be detached without breaking interior connections. The (H2(p-COOH)TPP = 5,10,15,20-tetrakis(4-carboxyphenyl)-
extensive and more detailed studies on polyrotaxane and porphyrin),564 and [Cu2(bpdc)2(phen)2(H2O)]2·2H2O.565
polypseudorotaxanes structures observed in MOFs have been Mode IB is topologically similar to mode IA, however, it
culminated by the pioneering scientists, Ciani, Kim, Robson, consists of side arms on either side of loops in opposite
Batten, Loeb, and others, with their commendable strategies to direction to produce an armed 2D polyrotaxane framework
develop a synthetic approach for this type of frame- (Figure 89b). An example in this case is [Cd(1,4-bdc)-
works.72,460,558−560 Notably, the inclusion of both flexible (Bpybc)1.5]·10H2O (H2BpybcCl2 = 1,1′-bis(4-carboxybenzyl)-
and long rigid ligands is desirable to attain polyrotaxanes in 4,4′-bipyridinium dichloride), in which Bpybc ligands form
which the former ligands act as closed 2-membered loops, both loops and rods along with Cd(II), whereas 1,4-bdc acts as
while the latter ones serve as rods which are interposed inside dangling side arms of the 1D chains (Figure 90b).566 The rods
the loops. Hence, we will not provide detailed account on this are penetrated inside the loops in an alternating fashion from
topic but rather focus on the types of different possibilities infinite such that 1D chains aligned in a grid and forms a 2D
through which 2D polyrotaxane MOFs have been observed architecture. This also forms a 3D pseudo-polyrotaxane MOF
with some relevant examples in each case. We will also discuss and exhibits thermochromic properties.
few 2D polypseudorotaxanes MOFs as well in this section. The third type which is mode IC is of a parallel kind unlike
The different possibilities to construct 2D polyrotaxane the inclined forms described above. Here, the 1D chains are
MOFs along with its involvement to form 3D MOFs are as interlaced in parallel into one another in an offset manner
follows: (i) 1D to 2D, (ii) 2D to 2D, and (iii) 2D to 3D (Figure 89c). For example, [Zn2(1,4-bix)3(SO4)2]·8H2O
structures. Batten et al. have illustrated different modes found exhibits a wavy 1D chain in which 1,4-bix ligand adopts
in each possibility, and we will follow the similar approach to gauche conformation and bridges adjacent Zn(II) centers
simplify the design principles for this form of structures.559 (Figure 91a).563 The last type, mode ID, displays entanglement
3.3.1. With 2-Connecting Ligands. 3.3.1.1. 1D to 2D of two different 1D chains A and B in which A consists of rod-
Polyrotaxane Structures. These structures arising from 1D like chains with dangling arms, whereas B consists of loops
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Figure 91. View of 1D to 2D (a) parallel and (b) inclined

entanglements with mode IC and mode ID, respectively. Adapted Figure 93. View of 2D to 2D polyrotaxane entanglements with (a)
with permission from ref 559. Copyright 2012 Royal Society of mode IIA and (b) mode IIB. Adapted with permission from ref 559.
Chemistry. Copyright 2012 Royal Society of Chemistry.

(Figure 89d). This has been observed in [Cu(bph)3(NO3)2]- revealed a 2D honeycomb sheet with same polyrotaxane
[Cu(bph)2(H2O)(NO3)]2·(NO3)2·EtOH (bph = 1,6-bis(4- structure in which tetrahedral Zn(II) centers coordinated to
pyridyl)hexane), with [Cu(bph)3(NO3)2] resembling A and bmimbp in syn-conformation and rigid tbtpa with both syn−syn
[Cu(bph)2(H2O)(NO3)]2·(NO3)2·EtOH similar to B.567 In A, and anti−anti modes.569 Similar relevant examples displaying
bridging bph ligands form the rods and two monodentate bph identical entangled form are provided in the litera-
acts as side arms, while in B, double bridging of Cu(II) centers ture.378,559,570−581
by bph forms chains of Cu2(bph)2 loops (Figure 91b). Figure In mode IIB, each single net is (4,4) connected with linear
91. loops of chains which are bridged by parallel rods on the
3.3.1.2. 2D to 2D Polyrotaxane Structures. Unlike the opposite sides and two such loops exhibit trans arrangement
previously mentioned structures, this type of polyrotaxane around the node (Figure 92b). Such type of arrangement is
frameworks are considered as nontrivial entanglements as these noted in [Cd(cpmb)(bbi)0.5(H2O)] (cpmb = 4-carboxy-
include interpenetration and thus cannot be disconnected phenylene-methyleneamino-3-benzyl acid; bbi = 1,4-bis(1H-
without separation of links. These have also been classified into imidazol-1-yl)butane), which is composed of 1D loop-like
four modes as illustrated in Figure 92. chains formed by the interlinkage of [Cd2O2] dimers through
double cpmb anions, and these are further bridged by long bbi
rods to the neighboring chains and furnish a 2D undulated
framework.582 The rod-like bbi ligand of one layer penetrates
through the [Cd2(cpmb)2] loops of the other resulting into a
2D to 2D MOF with 6-connected topology (22.49.64) (Figure
93b). The MOF [Zn(L2)(1,3-bdc)]·1.25H2O (L2 = 1,2-bis[3-
(4H-1,2,4-triazol-4-yl)phenoxy]ethane) also featured inter-
locking of two 2D polyrotaxane motifs in parallel fashion to
form 2D to 2D MOF.583
In this regard, Vittal and co-workers described a distortional
supramolecular isomerism due to change in the relative positions
of the threaded axles in the 2D polyrotaxane MOFs.584−586
The design approach involves two bent spacer ligands forming
wheels and two linear spacer co-ligands forming axles. The use
of V-shaped bent dicarboxylate, sdb and different dipyridyl
ligands bpeb, bpy, and bpe with Zn(II) and Co(II) yielded a
series of interesting 2D polyrotaxane MOFs of this type. This
involves [Zn2(bpeb)(sdb)2], [Co2(bpeb)(sdb)2], [Co2(bpy)-
Figure 92. Different modes of 2D to 2D polyrotaxane MOFs: (a) (sdb)2]·2H2O, and [Co2(bpe)(sdb)2]·DMA·1.5H2O with
mode IIA, (b) mode IIB, (c) mode IIC, and (d) mode IID. Adapted paddlewheel square cores [M2(O2C-C]4 bridged by sdb to
with permission from ref 559. Copyright 2012 Royal Society of
form a wheel that extends to form 1D loop-like chains and
Chemistry.
further interlinked by rod-like dipyridyl ligands in axial position
to create 2D MOF which further entangles with similar 2D net
In mode IIA, each loop in a 2D layer is connected to four and produce 2D to 2D with mode IIB (Figure 94). Some of
adjoining loops via four rods (Figure 92a). An example of this these showed 2D to 3D inclined polyrotaxane forms, which
type is [Co2(1,3-bix)2(bpea)2] (1,3-bix = 1,3-bis(imidazole-1- will be included in the next part of this section. Many other
ylmethyl)benzene), with flexible 1,3-bix and long rod bpea related examples are also decorated in the litera-
ligands. The [Co2(1,3-bix)2] loops are connected to rod-like ture.175,378,587−595
bpea ligands to form 2D structure, and the bpea ligands from Unlike mode IIB, in mode IIC, loop-like chains are arranged
one network penetrate into the loops of another sheet to in a cis-type zigzag fashion and the rods linking them are on the
generate 2D to 2D polyrotaxane architecture. Each 2D layer same side around each node (Figure 92c). An interesting CP
exhibits a hcb net, however, in terms of rotaxane-type of this type is [Zn3(OH)2(DHBBDC)2(bpy)(H2O)2]·H2O
interpenetration, each net is 4-connected with 2.65 topology (H2DHBBDC = α,α′-dihydroxybibenzyl-4,4′-dicarboxylic
(Figure 93a).568 The MOF, [Zn(bmimbp)(tbtpa)] (bmimbp acid) reported by Gao et al. A 2D sheet is generated by the
= 4,4′-bis(2-methylimidazol-1-ylmethyl)biphenyl; H2tbtpa = linkage of Zn3(μ2-OH)2(μ2-COO)2] units formed by bridging
tetrabromoterephthalic acid) reported by Sun et al. also of Zn(II) centers via carboxylate oxygen atoms from different
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Figure 96. View of parallel 2D to 2D polyrotaxane MOF with mode

IID. Adapted with permission from ref 559. Copyright 2012 Royal
Society of Chemistry.

Figure 94. (a−d) Schematic representation and view of the rotaxane

units with relative alignments of wheel and axle in two supramolecular
isomers [Zn2(bpeb)(sdb)2] with 2D to 2D parallel entanglement.
Reproduced with permission from ref 584. Copyright 2014 John
Wiley & Sons. View of isoreticular polyrotaxane 2D MOFs: (e,f)
[Co2(bpy)(sdb)2]·2H2O and (g,h) [Co2(bpe)(sdb)2]·DMA·1.5H2O.
Adapted with permission from ref 586. Copyright 2017 Royal Society
of Chemistry.

DHBBDC ligands and a hydroxo group to another DHBBDC

and bpy ligands (Figure 95). Here, large loops are built by

Figure 97. Schematic views of different modes for 2D to 3D

polyrotaxane entanglements: (a,b) mode IIIA, (c) mode IIIB, and (d)
mode IIIC. (a,b) Adapted with permission from ref 587. Copyright
2009 Royal Society of Chemistry. (c,d) Reproduced with permission
from ref 559. Copyright 2012 Royal Society of Chemistry.
Figure 95. View of 2D to 2D polyrotaxane entanglement with mode and IID. This has been illustrated in [Zn 4 (1,2-
IIC. Reproduced with permission from ref 559. Copyright 2012 Royal
Society of Chemistry.
BBOMB)4(bpp)2] (1,2-BBOMB, a flexible V-shaped ligand)
containing two conformationally different [Zn 2 (1,2-
BBOMB)2] loops which are bridged by flexible bpp rods
DHBBDC ligands that pair up to doubly bridge the adjoining with TT and TG conformations to form a 2D net (Figure
trinuclear units and rod-like bpy penetrates the loops from 98).587 The loops from one 2D net entangle with bpp rods
another 2D net to afford 2D to 2D polyrotaxane framework
with 6-connected topology (22.49.64).596
The fourth type exhibits mode IID that is topologically
similar to mode IIB except for three-fold entanglement instead
of double leading to passage of two rods through each loop
(Figure 92d). When 1,3-BBOMB (1,3-BBOMB = 1,3-bis-
(benzoato-4-oxamethyl)benzene) in combination with Zn(II)
and bpy was used instead of 1,2-BBOMB, it led to the 2D
MOF [Zn2(1,3-BBOMB)2(bpy)] of this type. Each Zn(II)
dimers are bridged by two 1,3-BBOMB ligands to create loop-
like chains that further connected by rod-like bpy to form a 2D
net. Furthermore, each loop gets penetrated by two bpy to
generate triple 2D to 2D polyrotaxane structure (Figure 96).587 Figure 98. (a) Structural and (b) schematic views of the individual
Similar analogous structures have been reported.378,482,597 networks in [Zn4(1,2-BBOMB)4(bpp)2]. Adapted with permission
from ref 587. Copyright 2009 Royal Society of Chemistry.
3.3.1.3. 2D to 3D Polyrotaxane Structures. To achieve 3D
structure from 2D polyrotaxane frameworks with nontrivial
entanglements is very challenging and thus rare in the from the neighboring nets in a parallel offset fashion to
literature. The three different modes possible in this form as generate 2D to 3D structure. Cheng et al. reported that this is a
described by Batten et al. have been shown in Figure 97. In rare example of coexistence of polyrotaxane, polycatenane, and
Figure 97a,b, the schematic views for 2D to 3D parallel interdigitation (see section 3.4).
polyrotaxane entanglement (mode IIIA) are depicted. Mode IIIB depicts another form of parallel entanglement of
Topologically, mode IIIA is almost similar to mode IIB and 2D nets with relatively 90° rotation to construct 3D networks
mode IID, however, differs in the orientation of adjacent loops, (Figure 97c). Here, each loop of one sheet is penetrated by the
which is perpendicular in this case while coplanar in modes IIB other loop from another sheet instead of rod-like ligands as
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well as penetrated by the sheets below and above it. This is imidazolylphenyl)amine (Tipa) has been observed to form
found in [Co2(pcp)2(bpp)]·2CH3OH (pcp = 1,3-bis(4- 2D to 2D parallel entangled MOFs in which 4-membered
carboxy-phenoxy)propane) with paddlewheel motifs in which loops are present instead of 2-membered loops owing to the
pcp ligands bridges Co(II) dimers to form loops, and rod-like existence of a third linking arm from another ligand. For an
bpp ligands bridge the loops to form 2D sheets which on example, [Ni2(Tipa)2(1,4-bdc)2(H2O)2]·3.25H2O exhibits 3,4-
further threading in the aforesaid way generates 2D to 3D connected undulated 2D net with Ni2(Tipa)2 1D ladder-like
polyrotaxane MOF.598 chains bridged by 1,4-bdc and another monodentate 1,4-bdc
The third mode IIIC is generated due to inclined acting as an arm protruding out from one side of the net.599 As
entanglement but topologically similar to mode IIA, in which a result, two different windows Ni2(Tipa)2 and Ni4(Tipa)2(1,4-
each loop in a 6-membered 2D sheet is penetrated by a rod bdc)2 are created which are polythreaded in a parallel face-to-
from an inclined sheet and forming an unusual inclined 2D to face manner (Figure 100a,b). This MOF also shows 2D to 3D
3D polyrotaxane MOF. As depicted in Figure 97d, two rods
from inclined sheets (red and orange) passes through the
highlighted blue loop on opposite sides, whereas rods of blue
net on the other sides participate in rotaxane interactions with
loops from green and pink inclined sheets. The MOFs
[Cd2(L)2(1,4-bdc)(NO3)2]·2DMF (L = 4-amino-3,5-bis(4-
imidazol-1-ylphenyl)-1,2,4-triazole); [Cd4(1,4-bix)4(bpea)4]·
4H2O and [Ni(DPDBT)(1,4-bdc)]·(H2O)2 (DPDBT = 2,8-
di(pyridin-4-yl)dibenzo[b,d]thiophene) feature this type of
polythreading network in which bpea/1,4-bdc act as rods and
1,4-bix/L/DPDBT with curved geometries bridge Cd(II) to
form loops.495,568,576 Additionally, Vittal et al. demonstrated
parallel/diagonal inclined entanglement in polyrotaxane-based Figure 100. (a,b) Structure and schematic view of the 2D to 2D
rectangular 2D sheet to form 3D structure in [Zn2(bpeb)- parallel interpenetrating networks in [Ni2(Tipa)2(1,4-bdc)2(H2O)2]·
(sdb)2] and [Co2(bpeb)(sdb)2]·0.5DMA·2H2O.584,585 3.25H2O, respectively. (c) Schematic view of the formation of
3.3.1.4. Self-Threading Polyrotaxane Structure. An inter- rotaxane interactions by the interdigitation of adjacent sheets. (d−f)
esting MOF, [Cd 4 (sdb) 4 (bpmp) 3 ] (bpmp = bis(4- Structural and schematic view of 2D to 2D polyrotaxane
entanglement in [Cu4(Tipa)4(1,4-bdc)2(CH3OH)2(H2O)2]2(1,4-
pyridylmethyl)piperazine), was reported by Hong and co- bdc)3(CH3OH)8(H2O), respectively. (a−c) Adapted with permission
workers with a rare self-threading features.590 This can be from ref 599. Copyright 2011 Royal Society of Chemistry. (d,e)
regarded as a supramolecular isomer of Adapted with permission from ref 559. Copyright 2012 Royal Society
[Co4(sdb)4(bpmp)3(H2O)4]·2H2O which shows mode IIB of Chemistry. (f) Adapted with permission from ref 600. Copyright
entanglement. Notably, [Cd4(sdb)4(bpmp)3] consists of 2011 Royal Society of Chemistry.
tetrameric units Cd 4 (CO 2 ) 8 formed by bridging of
Cd2(CO2)4 paddlewheel cores with sdb2− rather than dimeric
units as observed in [Co4(sdb)4(bpmp)3(H2O)4]·2H2O. interdigitation (Figure 100c), which will be illustrated in
Further, Cd2(sdb)2 loops are linked by a pair of sdb2− that section 3.4. Another MOF, [Cu4(Tipa)4(1,4-bdc)2(CH3OH)2-
generate doubly stranded polymeric chains which are extended (H2O)2]2(1,4-bdc)3(CH3OH)8(H2O), is of similar type but
by bpmp bent rod-like ligands to generate the sql net structure. with different topology (Figure 100d−f).600
The penetration of bpmp ligands into the pairs of Cd2(sdb)2 3.3.2.2. 2D to 3D Parallel Polyrotaxane Structures. An
loops from opposite sides of the same net results in the example of this kind is [Cd(Tipa)Cl2]·1.07H2O, which
formation of a 2D to 2D non-interpenetrated self-threaded displays an undulated 2D net with fes topology. In this case,
structure (Figure 99). Cd2(Tipa)2 rings formed by two Cd(II) and four Ph-imidazole
3.3.2. With 3-Connecting Ligands. 3.3.2.1. 2D to 2D arms of two different Tipa ligands are penetrated by two rod-
Parallel Polyrotaxane Structures. Other than above men- like Tipa ligands from two adjoining networks below and
tioned types which involve 2-connecting ligands, polyrotaxane above it and furnished 2D to 3D offset parallel interpenetrated
structures with 3-connecting ligand such as tri(4- structures (Figure 101).601 Few other MOFs displaying 2D to
3D parallel entanglement have been reported.602,603

Figure 101. (a) Structural and (b) schematic views of 2D to 3D

Figure 99. Self-threaded polyrotaxane structure of parallel polyrotaxane entanglement in [Cd(Tipa)Cl2]·1.07H2O.
[Cd4(sdb)4(bpmp)3] and its schematic view. Reproduced with Adapted with permission from ref 601. Copyright 2011 Royal Society
permission from ref 590. Copyright 2014 Royal Society of Chemistry. of Chemistry.

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3.3.3. 1D + 2D and 2D + 3D Mixed Polyrotaxane

Structures. A recent study by Luo and co-workers illustrated
an unprecedented (3,4,5)-connected 3D paddlewheel frame-
work [NH2(CH3)2][Zn2(HL)L0.5]·8DMF·5H2O (H4L = 5,5′-
(1,3,6,8-tetraoxobenzo[lmn][3,8]phenanthroline-2,7-
(1H,3H,6H,8H)diyl)diisophthalic acid) featuring 1D rotaxane-
like chains interlocked in an inclined manner with a 2D layer
containing 38-membered Zn4(HL)2 rhombuses (Figure
102).604 It also exhibits controlled ibuprofen release activity.

Figure 104. Structures and schematic views of 2D loop-containing

and 3D pcu nets to form overall 2D + 3D to 3D framework. Adapted
with permission from ref 559. Copyright 2012 Royal Society of
Chemistry.

Figure 102. (a) Part of the structure showing self-threaded array

between 1D rotaxane-like chains and 2D rhombi nets. (b) 1D + 2D to
3D polyrotaxane structure of [NH2(CH3)2][Zn2(HL)L0.5]·8DMF·
5H2O. Adapted with permission from ref 604. Copyright 2014 Royal
Society of Chemistry.

Another interesting 1D + 2D to form 2D entangled structure

investigated by Zhang and co-workers is [Cd2(BCbpy)2(1,4-
bdc)Cl2][Cd(BCbpy)2(1,4-bdc)]·18H2O, with 1D loop-like Figure 105. Schematic views of polypseudorotaxane architectures in
chains threaded by 2-fold parallelly interpenetrated (6,3)- (a) [La(NO 3 ) 4 (H 2 O)(bpee)][bpeeH] and (b) [Ag(bpp)]-
connected hexagonal 2D layers (Figure 103).574 [Ag2(bpp)2(ox)](NO3). Adapted with permission from ref 460.
Copyright 2003 Elsevier.

also observed in [Ag(bpp)][Ag2(bpp)2(ox)](NO3) in which

(6,3)-connected 2D sheets are threaded by 1D cationic chains
(Figure 105b).607 The MOF [Mn(H2O)4(bpmp)][Mn2(ox)3]·
5H2O (bpmp = bis(4-pyridylmethyl)piperazine) also features
similar polythreading of anionic 2D hexagonal sheets by 1D
cationic chains.608 Another example of ionic polypseudorotax-
Figure 103. Schematic illustration showing the 2-fold parallel ane structure is [Zn(2-stp)(bpy)(H2O)(H2O)0.25]2[Zn(bpy)-
interpenetration of 2D networks and the interlocking of 1D chains (H2O)4]·4H2O (2-stp = 2-sulfoterephthalate), with 2D
and 2D networks. Adapted with permission from ref 574. Copyright corrugated anionic sql sheets stacked in AA mode penetrated
2014 Royal Society of Chemistry. by 1D linear cationic chains to form 3D architecture with
unprecedented (3,4,4)-connected topology.609 A recent study
by He et al. revealed a 1D + 2D to 3D polypseudorotaxane
A rare example of 2D + 3D polyrotaxane 3D framework has structure [Ni(L)(bpee)(H2O)]·[Ni0.5(bpee)0.5(H2O)2]·H2O
been illustrated by Su et al. in [CuI3(1,4-btx)3][{CuII(1,4- (H3L = 5-(3-carboxybenzyloxy)isophthalic acid) containing
btx)2}{PMo12O40(VO)2}]·H2O (1,4-btx = 1,4-bis(1,2,4-tria- ABAB stacked anionic 2D rectangular layers and cationic 1D
zol-1-ylmethyl)benzene).605 It comprises a 2D loop-containing chains.610
sheet built from two Cu(I) centers connected to two types of Zhang and co-workers illustrated two supramolecular
1,4-btx ligands as well as a 3D pcu net framework with Cu(II) isomers with stoichiometry [Cu2(pz)(CN)2]·[CuCN] featur-
centers, 1,4-bix ligands, and bivanadyl-capped, highly reduced ing 3D polypseudorotaxane structures by the penetration of
Keggin polyanions (Figure 104). Interestingly, the longest rods 2D [Cu2(pz)(CN)2] sheets with 1D [Cu(CN)] chains. One
of 3D net pass through every loop of the 2D net to form a 3D isomer exhibits (3,4)-connected Shubnikov-type (5,34) sheets
polyrotaxane architecture. arranged in ABAB mode while the other with typical (6,3)-
3.3.4. Polypseudorotaxane Structures. Apart from connected brick wall layers arranged in ABBA mode (Figure
polyrotaxane MOFs, polypseudorotaxane MOFs have also 106).611
been widely studied which belong to trivial entanglements. A unique example of a 2D polypseudorotaxane is
These fall under trivial entanglement with separable motifs in [CuI(bbtz)]5[BW12O40]·H2O based on α-Keggin type poly-
which loops are threaded by rods without any stopper at the oxometalate [BW12O40]5−, one loop-containing metal−organic
two ends of it. Here, we will only focus on few 2D MOFs chain unit and four types of Cu-bbtz chain-like moieties.612
based polypseudorotaxane structures. The loop-like 1D chains are threaded by the wave-like 1D
Rogers et al. described a MOF, [La(NO3)4(H2O)(bpee)]- chains at a nearly perpendicular orientation to form a 2D layer.
[bpeeH], in which parallel polythreading takes place between Furthermore, these 2D layers are parallelly stacked through
1D linear chains and corrugated 2D (4,4) sheets resulting into which the 1D wave-like chains pass and form a 3D
a 2D polypseudorotaxane architecture named as “molecular polythreading architecture. Li and co-workers reported an
Chinese blinds” (Figure 105a).606 Similar interesting feature is interesting 2D sql layered framework in [Cd 2 (m-
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Figure 106. Supramolecular 3D polypseudorotaxane isomers of [Cu2(pz)(CN)2]·[CuCN]. Reproduced with permission from ref 611. Copyright
2012 American Chemical Chemistry.

pdoa)2(dpa)3(H2O)] (m-H2pdoa = 1,3-phenylenedioxy diac- extended interdigitation takes place with the similar 2D
etic acid; dpa = 4,4′-dipyridylamine) anchored with alternating interdigitated sheet from the opposite side that resulted in
side arms. Such two oppositely oriented adjacent layers are 1D to 2D to 2D interdigitation.
mutually embedded to form a 2D embraced bilayer which Dangling groups in the 1D linear chains participate in
further stack parallelly in ABABAB staggered fashion with interdigitation. For example, the 1D CP [Cd(1,4-bdc)(2F-
dangling dpa groups projecting out from each sides of the 4spy)2(H2O)]·2F-4spy displays 2D interdigitation via 2F-4spy
sheet and generate a 3D polypseudorotaxane MOF.496 A ligands and also accommodates guest 2F-4spy molecules in
similar 2D to 2D polypseudorotaxane MOF is noted in between 1D chains with opposite orientation with respect to
[Co(CH3O-H2Ip)(Bip)] (CH3O-H2Ip = 5-methoxylisoph- adjacent chains (Figure 107). Such interdigitation facilities [2
thalic acid; Bip = 3,5-bis(imidazole-1-yl)pyridine).613 These
two complexes can also be regarded as interdigitated
frameworks (see section 3.4).
Recently, Lee et al. described a 2D polypseudorotaxane
structure [(μ4-Ag)2(C8@L)2(μ-C8)]·(CF3CO2)2 (L = A1/A2-
thiopyridyl pillar[5]arene; C8 = dinitrile guest, CN-
(CH2)8CN) along with its proposed pathway of formation.
This includes rarely observed threading of pillar[5]arene cavity
as well as cross-linking of 1D parallelly stacked pseudorotaxane
arrays by C8 guest which direct its formation. Therefore, the
adaptive arrangement of different motifs minimized the steric
hindrance to afford a 2D polypseudorotaxane.614 Some
frameworks also show polypseudorotaxane structure along
with interdigitation which will be discussed in Section 3.4.3.
3.4. Interdigitation
This is the last type of entanglement that will be illustrated in a
detailed manner in this section. Interdigitation refers to the
polythreading of digited motifs of finite length that project into
the voids of the adjacent sheets and positioned in a face-to-face
manner. It is different from interpenetration or polycatenation
because it does not involve any penetration. In some Figure 107. 1D to 2D interdigitated structure in [Cd(1,4-bdc)(2F-
exceptional cases, this also shows pseudo-rotaxane like 4spy)2(H2O)]·2F-4spy via 2F-4spy ligands. Reproduced with
interactions and exist along with interpenetration or poly- permission from ref 616. Copyright 2014 American Chemical Society.
catenation. The essential criteria for interdigitation is the
presence of dangling lateral side arms or coordinated ligand + 2] photochemical reaction between host and guest 2F-4spy
moieties that protrude out to have interaction with the molecules (discussed in section 4).616 Another linear 1D chain
neighboring motifs from another layer. Accordingly, we have is [Cd(tBu-iso)(pich)(DMF)]·2DMF (tBu-iso = 5-tert-butyl-
divided this section into four categories of interdigitation: (i) isophthalate; pcih = 4-pyridinecarboxaldehyde isonicotinoyl
1D to 2D, (ii) 2D to 2D, (iii) 2D to 3D, and (iv) mixed hydrazine) in which adjacent chains in ABAB sequence
dimensional. undergo interdigitation via DMF molecules linked to metal
3.4.1. 1D to 2D Interdigitated Structures. An centers.617 Further similar 1D zigzag chains involved in
interesting 1D U-shaped chain [Ag2(bga)2(pzdc)(H2O)] interdigitation exhibit [2 + 2] cycloaddition photochemical
(bga = benzoguanamine; H2pzdc = pyrazine-2,3-dicarboxylic reaction (see section 4).618
acid) has been reported by Huang et al., consisting of large Also, 1D ladder-like chains have been illustrated to exhibit
interstices between the neighboring bga ligands that allow the interdigitation. The ladder CP [Ag2(bpethy)5](BF4)2 reported
1D to 2D interdigitation between similar chains with dangling by Ciani et al. is anchored with side arm monodentate bpethy
bga ligands through N−H···N hydrogen bonding.615 Further ligands that propagates the interdigitation to a 2D layer
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structure (Figure 108a).619 Zhang et al. also reported a 1D

ladder polymer [Cd3(bpea)(phen)3(OH)3(H2O)]·0.5bpea·

Figure 110. (a) Space filling representation of 1D → 2D

interdigitated layer and (b) its schematic view. Reproduced with
Figure 108. Interdigitated 2D structures of 1D ladder-like chains in permission from ref 625. Copyright 2012 American Chemical Society.
(a) [Ag2(bpethy)5](BF4)2 and (b) [Cd(adc)(4-nvp)2(H2O)]. (a)
Adapted with permission from ref 619. Copyright 1999 Royal Society
of Chemistry. (b) Reproduced with permission from ref 621. Recently, Baudron and co-workers described two isostruc-
Copyright 2018 American Chemical Society. tural 1D ribbon-like polymers based on a unique ethyl-
enedithio-tetrathiafulvalene (EDT-TTF) derivative function-
4H2O interdigitated to a 2D structure in a zipper fashion alized with two adjoining 4-thiopyridine groups that can form
through significant C−H···π interactions between the aromatic 2D interdigitated framework. These CPs further exhibit
rings of adjoining ladders.620 The MOF [Cd(adc)(4- boosted electronic conductivity upon oxidation by iodine on
nvp)2(H2O)] (H2adc = acetylenedicarboxylic acid; 4-nvp = the surface.626
4-(1-naphthylvinyl)pyridine) features a double chain ladder 3.4.2. 2D to 2D Interdigitated Structures. Very few
1D polymer with axial 4-nvp ligands that project out from both structures are reported with 2D to 2D interdigitated structures.
sides of dimeric units of the ladder and eventually participate in Robson and co-workers described a 2D MOF [Cu(tcm)-
mutual interdigitation to create a 2D layered architecture (hmt)] (tcm = tricyanomethanide; hmt = hexamethylenetetr-
(Figure 108b).621 Similar relevant examples which involve amine) with (4,4) connected puckered rectangular sheets
interdigitation of 1D ladder polymers to 2D structures are based on tetrahedral Cu(II) centers. The rod-like free nitrile
[Cd2(tBu-ip)2(pcih)2] and [Cd2(ip)2(pcih)2], with adjoining groups present on the same side from one sheet penetrates
ladders arranged in an ABAB manner.617 through the rectangular cavities of the other, which makes the
Other than these, an example of 1D meso-helical nanotubular tcm units be in close proximity and result in interdigitation.
or step-ladder like polymer, [Cd2(ADC)2(bpp)3(H2O)]2· Similarly, a doubly interpenetrated puckered (4,4) connected
8H2O (ADC = 1,3-adamantanedicarboxylic acid), displaying sheet [Cu(tcm)(bpy)] was also reported by them, in which the
1D to 2D interdigitated architecture with bpp as side arms free nitrile groups in each sheet are present on opposite sides
(Figure 109).622 Similarly, [Zn(L1)(bpee)] (L1 = H2L1 = 5- alternately.488 Manson et al. described a 2D MOF [Mn-
(dca)2(pym)(H2O)] (pym = pyrimidine) with hanging cyano
groups responsible for the interdigitation.627
In a square grid 2D chiral MOF [Zn(nicotinate)2],
interdigitation occurs via stacking in AB fashion.628 Wang
and co-workers investigated two 2D MOFs, [Zn(1,4-bdc)-
(DMA)] and [Zn3(1,4-bdc)3(DMA)2], with (4,4) and (3,6)-
connected nets, respectively, to exhibit 2D interdigitation via
the coordinated bulky DMA molecule serving as dangling
ligands.97 An interesting example of 2D to 2D interdigitation is
Figure 109. 1D mesohelical to 2D interdigitated structure of observed in [Cd(btd)(L2)(H2O)]·H2O (H2L2 = 5-hydroxy-
[Cd2(ADC)2(bpp)3(H2O)]2·8H2O. Reproduced with permission 1,3-benzenedicarboxylic acid; btd = 1,10-bis(1,2,4-triazol-1-
from ref 622. Copyright 2010 American Chemical Society. yl)decane) with wavy rectangular sql net, each of which is
digitated directly by another neighboring sql net through L2
carboxylates.629 Ghoshal et al. also reported a 4-connected 2D
(benzyloxy)isophthalic acid) with open-ended tubular 1D MOF, [Mn(azpy)2(NO2-1,4-bdc)]2, with dangling azpy
structure exhibits 2D interdigitated framework controlled by ligands that display a unique 2-fold interdigitated 2D layered
hydrogen bond interactions.623 structure.630 On the other hand, [Co(HL)(biim-4)] (H3L = 5-
Another set of MOFs to show 2D interdigitation are based (2-carboxybenzyloxy) isophthalic acid; biim-4 = 1,1′-(1,4-
on 1D ribbon-like chains. The MOFs [Cu(dca)2(4-cypy)2] butanediyl)bis(imidazole)) with corrugated double layers
and [Cu(dca)2(3-cypy)2] (dca = dicyanamide; cypy = interdigitated via face to face C−H···π interactions.631 A
cyanopyridine) with octahedral Cu(II) centers reported by wavy 2D rectangular sheet [Cd(NO 3 ) 2 (4-bpmhz) 3/2 -
Du and co-workers exhibit 1D to 2D interdigitation between (MeOH)]·0.5H2O (4-bpmhz = 1,2-bis(1-(pyridin-4-yl)-
the free nitrile groups from 4-cypy and 3-cypy alternately.624 ethylidene)hydrazine) with “parquet floor” topology displays
Another group of MOFs has been demonstrated by Xing et al. 2D to 2D interdigitation between three similar nets.632
in which 1D loop-like chains are half penetrated by rod-like L2 3.4.3. 2D to 3D Interdigitated Structures. Several
ligands of neighboring chains to form (3,4)-connected 2D MOFs were observed to exhibit 2D to 3D interdigitated
interdigitated layer (Figure 110), which in turn also exhibit 2D frameworks. In this context, Yaghi et al. investigated a 2D
to 3D perpendicular polycatenation.625 honeycomb framework [CoC6H3(COOH1/3)3(NC5H5)2]·2/
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3NC5H5 based on benzene tricarboxylate with pyridyl groups

dangling from alternating layers that allow for the interdigi-
tation.633 The 2D MOF [Ag(3,3′-DCPA)2]AsF6 (3,3′-DCPA
= 3,3′-dicyanodiphenylacetylene) featuring 2D helical chiral
polymer with tetrahedral Ag(I) center and cisoid-3,3′-DCPA
ligand has been revealed to display unique interdigitation
between a set of two interpenetrated helices (Figure 111).634

Figure 112. (a) View of 3D π-stacked with interdigitated layer

structure in [Cu(dhbc)2(bpy)]·H2O. Adapted with permission from
ref 635. Copyright 2003 John Wiley & Sons. (b) Representation of
selective guest sorption of a coordination polymer with interdigitated
structure. (c) 2D layered structure and (d) 3D assembled
interdigitated structure of CID-1@DMF. Adapted with permission
from ref 637. Copyright 2007 Royal Society of Chemistry.

di(4-benzoic acid)), based on a V-shaped H3 pidpa ligand

which interlinks the 1D chains formed by Tb(III) and bridging
carboxylates. This results in the uncoordinated imidazole and
pyridyl groups which direct the formation of 3D interdigitated
structure (Figure 113).649 In addition, a series of 2D MOFs

Figure 111. Interdigitation between two interwined helices in

[Ag(3,3′-DCPA)2]AsF6. Reproduced with permission from ref 634.
Copyright 1997 American Chemical Society.

Lin et al. investigated a flat 2D sheet with triangular units,

[Cd3(μ3-OH)L3(py)6](ClO4)2 (L = 4-[2-(4-pyridyl)ethenyl]-
benzoate), to display 3D interdigitated structure through
coordinated pyridyl groups projecting out from adjacent
layers.96
Kitagawa and co-workers illustrated several 2D MOFs based Figure 113. 2D to 3D interdigitation in MCF-53(Tb/Eu x).
on different linear bipyridyl and dicarboxylates with mutually Reproduced with permission from ref 649. Copyright 2017 American
Chemical Society.
interdigitated. The 2D MOF [Cu(dhbc)2(bpy)]·H2O (Hdhbc
= 2,5-dihydroxybenzoic acid) exhibiting 2D square grid layer in
which dhbc benzene planes are placed in upright fashion with based on different metal centers (M = Mn, Zn, Co, and Cd)
π···π stacking and thereby forming interlocked 3D structure and tetracyanoquinodimethane dianion (TCNQ2−) in the
with 1D channel (3.6 × 4.2 Å) containing ridges and hollows presence of pyridine-based co-ligands such as pyridine, 4-
(Figure 112a). This results in gated channels in the framework methylpyridine, quinoline, and 4-phenylpyridine also afforded
with potential sorption properties.635 Similar to this, another 2D to 3D interdigitated structures.650,651 Additionally, several
bilayered 2D MOF [Ba(μ2-OH2)(sdb)(H2O)3]·0.5H2O with 2D MOFs with corrugated layers were also noted to exhibit
uncoordinated carboxylate and phenyl groups from sdb ligand interdigitated 3D architectures.652−658
was reported by Xiao and co-workers.636 A stable 3D MOF Few other 2D MOFs are reported which exhibit coexistence
derived from the assembly of interdigitated 2D MOFs of parallel interpenetration, polypseudorotaxane or interdigita-
[Zn2(ip)2(bpy)2]·DMF (CID-1@DMF) with hydrophobic tion entanglements to form 3D aggregates. The combination of
walls decorated by ip and bpy has been described by polypseudorotaxane, interpenetration and interdigitation pro-
Kitagawa’s laboratory (Figure 112b−d). In this case, nearby moting hydrogen bond interactions has been investigated in a
ip ligands mutually digitate due to lack of π···π interaction and 2D MOF, [Zn(1,2,4-Hbtc)(bpy)] (1,2,4-btc = 1,2,4-benzene-
thus assists in the guest adsorption.637,638 Similar interdigitated tricarboxylate). The structure has a rhombic grid composed of
2D MOFs were also reported.639−645 Apart from these, some lateral arms from bpy ligand with layers stacked in ABAB
2D MOFs interdigitated to 3D structure have been utilized for sequence.659 These dangling pyridyl groups act as rods to
the fine tuning of the [2 + 2] photochemical cycloaddition promote the threading into the wheel-like rhombic windows in
reaction.646−648 an inclined fashion as well as pair up to digitate with another
Zhang et al. reported a series of lanthanide and mixed pair from adjacent layer. In a similar manner, Bai et al. have
lanthanide 2D MOFs, [Tb1−0.0 1xEu0.01x(Hpidba)(HCOO)- reported a fascinating tri-layered framework [Cd-
(H2O)0.5(HCOOH)0.5]·3H2O (MCF-53(Tb/Eux), x = 0, 3.4, (C4O4)2(H2O)2][Cd(C4O4)0.5(Hbpee)(H2O)3] based on two
21.4, 33.7 and 100) (H3pidpa = 2-(2-pyridyl)-1H-imidazol-4,5- types of anionic and cationic (without and with hanging
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monoprotonated Hbpee+ side arms) 2D square grid sheets

arranged in ABAB fashion, which show the coexistence of
aforesaid polythreading motifs (Figure 114).660 The difference

Figure 114. (a) Structure of [Cd(C 4 O 4 ) 2 (H 2 O) 2 ][Cd-

(C4O4)0.5(Hbpee)(H2O)3] with triple-layer 3D polythreading net-
work and (b) interpenetration in triple-level sheets. Adapted with
permission from ref 660. Copyright 2009 Royal Society of Chemistry. Figure 116. (a,c) 2D to 2D interpenetration and (b,d) 2D to 3D
interdigitation in [Zn(btd)(L2)]·H2O and [Zn(Hbtc)(L1)]·4H2O,
between the two is that in the former case interpenetration respectively. (a,b) Adapted with permission from ref 629. Copyright
takes place between one type of layer, whereas triple level 2014 Royal Society of Chemistry. (c,d) Adapted with permission from
sheets interpenetrate in the latter case. Another similar ref 662. Copyright 2013 Royal Society of Chemistry.
squarate-based tri-layered 2D MOF [Zn(Hbpee)-
(C4O4)0.5(H2O)3][Zn(C4O4)2(H2O)2] is also documented in framework [Cu6(pybz)8(OH)2]·I5−·I7− (pybz = 4-pyridylben-
the literature.144 zoate) inclusive of polyiodide anions and dangling pyridyl side
Only polypseudorotaxane and interdigitation has been arms directed by the introduction of iodine molecule as a
observed in some undulating 2D MOFs such as versatile precursor template via hydrothermal synthesis.663 It
[Zn2(HL)2(biim-3)2]·3H2O (H3L = 5-(2-carboxybenzyloxy) has been employed as a modulated probe molecule to analyze
isophthalic acid; biim-3 = 1,1′-(1,3-propanediyl)bis- the electrical conductivity and NLO properties before and after
(imidazole)). This MOF has two sets of wavy layers formed iodine release. Two interesting examples of isomorphous 2D
by (a) Zn1 linked to HL1 and biim-3A ligands and (b) Zn2 self-penetrated MOFs, [M(oba)(dpa)]·H2O (M = Ni; Co)
connected to HL2 and biim-3B ligands. These layers combined (H2oba = 4,4′-oxybis(benzoic acid; dpa = 4,4′-dipyridyl-
with the uncoordinated HL ligands as lateral arms to amine), with an unprecedented non-diamond 66 topology
interdigitate as well as penetrate into the windows of the displaying 3D interdigitated frameworks have been reported by
adjacent layers serving as polypseudorotaxane (Figure 115).631 LaDuca et al.664 These are made up of double helices
[M(oba)]n connected through [M(dpa)]n corrugated chains.
Adjoining self-penetrated layers interdigitate, which further aid
in hydrogen-bonding between N−H groups from dpa amine
and ligated carboxylate oxygen atoms from alternate layers
(Figure 117).

Figure 115. Coexistence of 2D to 3D interdigitation and

polypseudorotaxane in [Zn2(HL)2(biim-3)2]·3H2O. Adapted with
permission from ref 631. Copyright 2012 Royal Society of Chemistry. Figure 117. (a) Self-penetrated layers and (b) 2D to 3D
interdigitation in [Ni(oba)(dpa)]·H2O. Adapted with permission
from ref 664. Copyright 2007 American Chemical Society.
In a similar way, the Co(II) MOF, [Co(bpt)(Htma)(H2O)]
(bpt = 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole; H3tma =
trimesic acid), with each corrugated (4,4)-connected sheet 3.4.4. Interdigitation with Mixed Dimensional Struc-
consists of a free carboxylate from a bpt ligand positioned tures. In this part, we will discuss the examples involving
above and below it and simultaneously gets inserted into the combination of 2D MOFs with other dimensional structures to
adjoining network.661 Analogous entanglement is also noticed result in interdigitation between mixed dimensional motifs.
in another 2D MOF.662 Fujita et al. described an unusual and interesting trilayered
The amalgamation of interpenetration and interdigitation is framework, [Cd(L)2(NO3)2][Cd4(L)4(NO3)6(MeOH)6][Cd-
noted in [Zn(btd)(L2)]·H2O (H2L2 = 5-hydroxy-1,3- (L)(NO3)3](NO3)·2(mesitylene)·3MeOH (L = 4,4′-bis(4-
benzenedicarboxylic acid) and [Zn(Hbtc)(L1)]·4H2O (L1 = pyridyl)biphenyl), comprising the expected 2D square grids
1,6-di(1,2,4-triazol-1-yl)hexane) exhibiting wave-like rectangu- [Cd(L)2(NO3)2] (A) of dimension 20 × 20 Å2, cationic
lar 2D sheets.629,662 Here, both MOFs show 2D to 2D double linear chain [Cd4(L)4(NO3)6(MeOH)6]2+ (B), and a
interpenetration and protonated carboxylate groups projecting cationic linear chain [Cd(L)(NO3)3]− (C) (Figure 118).665
out from alternate layers directs the 2D to 3D interdigitation Also, a 3D-polyrotaxane type arrangement is obtained due to
(Figure 116). Other examples of this kind include two the insertion of double linear chains into the channels created
supramolecular isomers with (4,4)-connected net.495 from the packing of grid A. Interestingly enough, the same
Zeng and co-workers have exemplified a unique 2D to 3D arrangement is obtained for other two guest molecules, m-
interdigitated and interpenetrated double-pillared bilayer xylene and o-xylene.
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Figure 118. Illustrations for the three coordination polymers

exhibited in the crystal structure of [Cd(L) 2 (NO 3 ) 2 ]-
[Cd 4 (L) 4 (NO 3 )6 (MeOH) 6 ][Cd(L)(NO 3 ) 3 ]·NO 3 ·2(mesitylene)·
3MeOH: (a) square grid (A), (b) double linear chain (B), and (c)
linear chain (C) to form a 3D-interdigitated and polyrotaxane
framework. Adapted with permission from ref 665. Copyright 2002
Royal Society of Chemistry.

Figure 119. Illustrations for the two coordination polymers observed

in the crystal of [Cu(tp)(bpt)(H2O)]2[Cu(bpt)2(tp)]·2H2O: (a) 1D
Another example involves the combination of a puckered 2D polymeric chain, and (b) 2D (4,4) sheet. (c) Schematic
representation showing the interdigitated polythreading of the 1D
(4,4)-connected net MOF interdigitated with 1D zigzag chains
chains (yellow) and 2D layers (purple, blue, and red). The tp and bpt
[Cd2(bpea)(pt)(phen)2][Cd(pt)(phen)]·2H2O (pt = phtha- linkers are simplified only as the rods for clarity. Adapted with
late).620 This consists of a long and narrow window formed by permission from ref 667. Copyright 2005 Royal Society of Chemistry.
alternating pt and phen linked to dinuclear unit that allows for
the interdigitation by phen dangling ligands. On the other 4. STRUCTURAL TRANSFORMATIONS
hand, [Zn 2 . 5 (L) 4 (μ 3 -OH)]·5H 2 O (L = 3-{[4-(4-
pyridylethenyl)phenyl]ethenyl}benzoate) has both interdigi- Structural transformations in MOFs can be divided, in general,
tated 1D chains with bridged hydroxy groups and inter- into two categories. In the first category, removal of guest
penetrated 2D rhombic grids.666 The dangling pyridyl ligands solvents from crystal lattice usually triggers structural
(L-N2) from 1D chains get inserted inside the voids of 2-fold distortions and movements such as sliding and compression.
interpenetrated 2D sheets, while the bent pyridyl ligands (L- This does not involve any bond formation or bond breaking.
N4) from 2D grid fill the empty space between the adjoining These structural changes modify the surface area, size, and
1D chains to result in interdigitation. In the 2D MOF shape of the pore. Because of structural flexibility of the highly
[Cu(tp)(bpt)(H2O)]2[Cu(bpt)2(tp)]·2H2O (tp = terephthalic ordered networks, these are often called “soft crystals” or
acid; bpt = bis(4-pyridyl)-4-amino-1,2,4-triazole), the 1D “dynamic crystals”.669−675 Kitagawa classified such crystals as
linear chains [Cu(bpt)2(tp)] with side arms bpt located at third generation porous coordination polymers (PCPs).669−672
opposite directions alternately, digitate into the (4,4)- On the contrary, in the second category, a solid-state
connected net [Cu(tp)(bpt)(H2O)]2 in an inclined manner structural transformation in MOFs arises from a chemical
to form a 1D + 2D to a 3D interdigitated array (Figure reaction and involves in a new bond formation and/or a bond
119).667 It can also be regarded as a polypseudorotaxane breaking. This is often triggered by the removal of coordinated
polythreading arrangement. molecules at the metal centers and/or guest lattice solvents
Wang and co-workers also reported a 3D framework, under vacuum or exchange of solvents, heat, or light.676−686
[Co(dpe)(btc)(H 2 O)][Co(dpe)(btc)(H 2 O) 3 ][Co(dpe)- These are different and distinct from the normal solid-state
(Hbtc)(H2O)][Co(dpe)2(H2O)3.5(EtOH)0.5]·1.5H2O (dpe = reactions. In the crystals, the molecules pack with both short-
1,2-bis(4-pyridyl)ethane), comprised multidimensional poly- and long-range ordering. In several solids, the reactive
mers, i.e., two (4,4)-connected 2D MOFs of anionic [Co- functional groups are predisposed closely in the required
(dpe)(btc)(H2O)]− and neutral [Co(dpe)(Hbtc)(H2O)] and “transition state” assisted by the supramolecular interactions,
two 1D polymeric chains of anionic [Co(dpe)(btc)(H2O)3]− so that the reaction can be triggered by external stimuli leading
and cationic [Co(dpe)(H2O)3.5(EtOH)0.5]2+.668 Here, two to the structural rearrangements. Such topochemical reactions
rectangular anionic and neutral 2D grids with distorted take place and assisted by various weak intermolecular
octahedral Co(II) centers and anti-dpe are mutually interactions and crystal engineering principles. The positions
interdigitated with each other via the uncoordinated of the atoms will not move drastically after the reaction and
carboxylate group from lateral btc3− and Hbtc2− and form hence single crystals will be maintained in the product. This is
double-layered networks arranged in parallel ABAB fashion to known as “single-crystal-to-single-crystal” (SCSC) reactions.
generate 1D rectangular channels. These channels get further 4.1. Dynamic Behavior of Soft Crystals
threaded by the 1D linear chains containing distorted These structural transformations take place without any
octahedral Co(II) centers and anti-dpe arranged in an alternate chemical reaction. The reversible dynamic structural changes
fashion to generate a 3D supramolecular framework which is due to light, heat, pressure, and in the presence of small
strongly entangled via both hydrogen bonding as well as π···π molecules are very interesting and important in gas sorption
interactions. This exhibits reversible rehydration/dehydration (gating) and separation. The detailed accounts on this dynamic
chromic activity upon exposure to heat and water vapor due to behavior of PCPs have been described in several scholarly
structural transformation. reviews by Kitagawa, Férey, and others669−675,687−690 The
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major structural changes in 2D MOFs involves compression EtOH to one of the thiocyanate ligands. The hydrogen-bonded
and expansion or sliding of interlayers.688,689 These are Fe(II) core exhibits SCO behavior at 150 K as high spin (S =
illustrated with an example below. 2) Fe(II) changed to low spin state (S = 0). After the removal
Biradha and Fujita described an example for the breathing of of the EtOH guest, the desolvated compound where the two
a 2D MOF. A doubly interpenetrated (10,3)-b net, Fe(II) are equivalent, does not show SCO behavior. Here the
[(ZnI2)3(tpt)2]·6C6H5NO2, shrinks when the nitrobenzene reversible structural changes caused by the absorbed guests
guest molecules are removed from the channels and swells changed the magnetic properties, thus making this suitable for
when they are returned (Figure 120).691 Such breathing of molecular sensing.
MOFs have been frequently encountered in the literature. The Realizing time scale as an adjustable dimension in porous
sliding of layers by the guest molecules has also been reported MOFs, which are attributed to the structural dynamics in soft
by the same authors.109 crystals, they have been termed as four-dimensional MOFs.694
4.2. Transformations Induced by the Removal of
Coordinating Solvents
When coordinated solvents are removed from the metal
centers, they try to satisfy the coordination number and
geometry by binding to the freely available atoms that can
donate a pair of electrons. In most of the structural
transformations, bond formation occurs between the metal
Figure 120. Breathing of a MOF via reversible solvation−desolvation centers and free uncoordinated atoms, such as a carbonyl
process.
oxygen atom of the carboxylate ligands after the loss of
If the 2D layers are soft and structurally flexible, the coordinated solvents. The new bond formation may be
structural transformation can be affected by the intralayer between intralayers, interlayers, or with the guest ligands in
distortion and interlayer compression by the loss of guest the lattice. The reaction between the interlayers promotes
molecules. Chen et al. reported a 2D MOF [Cu2M- increase in dimensionality while intralayer reactions generates
(tzdc)2(H2O)2]·2H2O (M = Fe(II) or Mn(II); tzdc = 1,2,3- structural rearrangement. This section deals with such
triazole-4,5-dicarboxylate) to have mixed-spin microporous examples from the literature.
Kagomé layers, arising from different metal ions.692 Both 4.2.1. 0D to 1D to 2D Transformations. A change in the
coordinated and lattice water molecules could be removed by dimensionality was demonstrated from a discrete (0D)
heating the solid to 300 °C (Figure 121). The solid-state coordination complex [Co(bpy)2(CH3CN)2(H2O)2]·2(OTf)
to 1D polymeric chain [Co(bpy)(OTf)2(H2O)2]·(bpy) (OTf
= trifluoromethanesulfonate, triflate) and then finally to a 2D
square-grid sheet [Co(bpy)2(OTf)2] (Figure 122).695 The
mononuclear octahedral Co(II) center is bonded to two bpy,

Figure 121. Structural changes around coordination environment of

(a) hydrated and (b) dehydrated [Cu2M(tzdc)2(H2O)2]·2H2O. (c,d)
Change in packing of the Kagomé layers viewed along b-axis during
dehydration−rehydration process. Reproduced with permission from
ref 692. Copyright 2010 American Chemical Society.

structure reveals that a reversible structural transformation

takes place from the microporous to nonporous structure by
intralayer wrinkling and interlayer compression. This “soft-
crystal” showed a reversible change in magnetism between the
ferrimagnetic character of the hydrated samples and the
suppressed ferrimagnetic character of the dehydrated samples
during this reversible dehydration and rehydration.
The following example illustrates how the magnetic
properties, specifically, the spin-crossover (SCO) behavior, is
influenced by the change in the coordination and local
electronic environments due to the loss of guest solvents
during structural transformation.693 In the diagonally inter- Figure 122. Stepwise structural conversions from 0D complex
penetrated 2D MOF with rhombic (4,4) net, [Fe- [Co(bpy)2(CH3 CN)2(H2O)2]·2(OTf), through 1D CP, [Co-
(azpy)2(NCS)2]·EtOH, the two octahedrally coordinated (bpy) 2 (CH 3 CN) 2 (H 2 O) 2 ]·2(OTf), to form 2D MOF [Co-
Fe(II) centers are inequivalent due to hydrogen bonded (bpy)2(OTf)2].

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two OTf ligands and two aqua ligands in trans manner. When [Cu2(pht)2(im)4]·H2O (pht = phthalate) were obtained in 2
the orange single crystals of the metal complex were kept in days (Figure 124).222 The hydrolyzed 2D MOF consists of two
humid air, it spontaneously lost the coordinated CH3CN to a
pale-pink powder. The coordination bond of one monodentate
bpy ligands was detached to become a guest molecule and the
second coordinated bpy bridge two Co(II) centers. The bpy
ligands undergo dynamic rotation by maintaining orthogonal
orientation to form 1D polymeric chain. The nitrogen atoms of
the bpy ligands which was hydrogen bonded to the aqua ligand
now bridges Co(II) centers to form 1D chains. The structure
of the pink powder was determined from the PXRD data, and
Figure 124. Structural transformation from 0D complex, [Cu-
the guest bpy molecules are hydrogen bonded to the aqua
(cmb)2(im)2] to 2D Cu(II) MOF, [Cu2(pht)2(im)4]·H2O, by
ligands of the 1D chains. Upon dehydration at 150 °C, the 1D hydrolysis. Adapted with permission from ref 222. Copyright 2014
chain undergoes a second structural transformation by forming Royal Society of Chemistry.
new Co−N bonds from the “guest bpy” after the loss of
coordinated water. Thus, the double structural transformation
occurs via a dynamic process involving cooperative movements different hexacoordinated Cu(II) centers: one coordinated to
of the ligands, anions, and guest molecules. This is very similar two imidazole ligands and three phthalate groups with
to that reported in [Co(μ-bpy)(NCS)2(H2O)2]·(bpy) by monodentate (η1:η0) and bidentate (η1:η1 and μ2-η2:η1)
Jacobson et al. before.124 Another 1D CP [Cu(bpy)- binding modes while the other center bears a coordinated
(H2O)2(BF4)2]·(bpy) also found to undergo structural water, two imidazole ligands, and two phthalate groups with
conversion to a 2D [Cu(bpy)2(BF4)2] by the removal of two η1:η0 and μ2-η2:η1 binding modes. The hydrolysis of the mono
trans aqua ligands similar to the transformation described ester converted the mononuclear single crystals and the
above.696 formation of the 2D MOF is accompanied by change in the
4.2.2. 0D to 2D Transformations. A light-purple chemical composition and hence likely to occur via dissolution
trinuclear complex, [Ni3(Hptz)6(H2O)6]·9H2O (H2ptz = 4- and recrystallization of the final product.
(1,2,4-triazol-4-yl)phenylphosphonic acid), under hydrother- The loss of coordinated water and 2/3 of 1,4-dioxane ligands
mal conditions in aqueous acetic acid at 180 °C for 7 h from the Cu(II) metal complex, [CuCl 2 (1,4-dioxa-
converted to a green 2D MOF, [Ni(Hptz)2]·7H2O (Figure ne)2(H2O)2], upon heating at 120 °C, yielded the 2D MOF
123).697 In the trinuclear complex, three Ni(II) atoms are μ1,2- [Cu3Cl6(1,4-dioxane)2] in an SCSC fashion.698 The 2D MOF
is formed when the terminal chloride ions bridge the Cu(II)
atoms. It is made up of 1D CP with Cu(μ-Cl)2Cu rings. In this
chain, two successive Cu(II) atoms have distorted square-
pyramidal geometry with one dioxane ligand and the third
Cu(II) atom has octahedral geometry with two dioxanes. The
bridging of dioxanes across Cu2Cl4 polymeric chains yielded
the 2D structure. The 0D to 2D structural rearrangement was
further accompanied by the observed change in magnetic
properties. In another discrete metal complex, [Co(bpip)3Cl2]2
(bpip = N,N-bis(3-pyridyl)isophthalamide), CoCl2 is cleanly
replaced by HgCl2 in an SCSC manner to [Hg(bpip)Cl2]2 by
immersing the single crystals in a methanolic solution of
HgCl2.699 But when CdSO4 is used instead of HgCl2, the
Co(II) complex is transformed to a 2D MOF, [Cd(bpip)-
(SO4)(H2O)2] (Figure 125). This transformation seems to be
accompanied by “recurrent dissolving−exchange−recrystalliza-
tion process” as supported by scanning electron microscopy
Figure 123. Structural transformation from 0D complex, and hence this is not an SCSC process.700
[Ni3(Hptz)6(H2O)6]·9H2O, to 2D Ni(II) MOF, [Ni(Hptz)2]·7H2O. The Co(II) complex, [Co2(qoac)2(N3)2(H2O)2] (qoac =
quinolone-8-oxy-acetate) is a centrosymmetric double end-on
bridged by six Hptz ligands and each terminal Ni(II) is bonded azido-bridged dimer.701 The aqua ligands are hydrogen
to three aqua ligands in a facial manner. In the 2D MOF, the bonded to the carboxy oxygen atom of the adjacent dimer
μ1,2-triazolate bridged [Ni2(μ-Hptz)4] chains are further μ1,2- [O−H···O, 2.66 Å] as well as to an azido nitrogen. This creates
bridged by the phosphonate ligands. Overall, one-third of a hydrogen-bonded (4,4) network structure. The aqua ligands
phosphonates are coordinated. This 2D MOF exhibits are lost when the single crystals are heated to 150 °C under
excellent chemical stability as well as higher CO2 adsorption vacuum. In this topochemical process, the uncoordinated
and separation compared to N2 at room temperature. intermolecular carboxy oxygen atoms occupy the empty sites,
Hydrolysis of esters has been used to assemble 2D MOF thus resulting in the formation of a 2D MOF. Drastic change in
from the metal complexes. When the dark-blue single crystals the magnetic properties were observed during this SCSC
of the mononuclear Cu(II) complex [Cu(cmb)2(im)2] (cmb = reaction. A strong interdimer ferromagnetic coupling is
2-carbomethoxybenzoate and im = imidazole) were moistened exhibited by the 0D complex. Interestingly, a spin-canting
with a small amount of aqueous methanol and kept in open antiferromagnetic ordering due to anti−anti carboxylate
atmosphere, light-blue crystals of the 2D MOF bridges was observed by the 2D MOF.
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removal of the coordinated methanol resulting in a 2D MOF,

[Pb(8-Quin)(NO3)].704 The 1D CP is made up of tetranuclear
[Pb4(μ-8-Quin)4(MeOH)2] repeating units, which are further
bridged by nitrate anions. When the MeOH coordinated to the
Pb(II) is removed by heating, the vacant coordination site has
been replaced by an unused oxygen atom of the nitrate ligand
chelated to Pb(II) from the adjacent strand. In addition, the
coordination bond between the O of 8-Qiun and Pb(II) is also
disrupted and displaced by the third oxygen atoms of the μ1,3-
bridging nitrate. The coordination number of Pb(II) atoms
was retained during this SCSC transformation. The trans-
formation was achieved by an unusually high temperature (160
°C) and 3 days of long heating time. Further, this 1D to 2D
structural conversion was found to be reversible as monitored
by the PXRD studies.
A conformational changes in the flexible ligand, 1,4-
Figure 125. Reaction of a metal complex, [Co(bpip)3Cl2]2 with bis(triazol-1-ylmethyl)benzene (btix), is responsible for non-
CdSO4, leading to structural transformation to 2D sheets, [Cd(bpip)- SCSC and irreversible 1D to 2D structural transformation
(SO4)(H2O)2]. (Figure 127).705 In the isostructural CPs [M(btix)2(H2O)2]-

The colorless crystals of [Tb(DMSO)8][Cu2I5] slowly

decomposed at room temperature after several days, into a
purple-colored mixture.702 From this mixture, [Tb(DMSO)8]-
[CuI3][I] and [Tb(DMSO)8](I)2(I3) were isolated and
structurally characterized. The deliquescent crystals of [Tb-
(DMF)8][CuI3][I] further undergo solid-state structural
transformation in Paratone oil to furnish [Tb(DMF)6(H2O)3]-
[CuI7CuII2I14]. The [CuI7CuII2(μ3-I)8(μ-I)6]3− anion has the
sheet structure in which the Tb(III) cations are encapsulated.
4.2.3. 1D to 2D Transformations. Removal of single
crystals from the mother liquor results in a facile SCSC
transformation of a 1D ladder structure, [Pb(ebdc)(MeOH)]·
H2O, to 2D MOF, [Pb(ebdc)] (ebdc = 5-ethynyl-1,3-
benzenedicarboxylate) (Figure 126).703 In the 1D ladder

Figure 127. 1D to 2D structural transformation in [M-

(btix)2(H2O)2](NO3)2·2H2O upon thermal dehydration via con-
formational changes of flexible ligand btix.

(NO3)2·2H2O (M = Co or Zn), the metal center is bridged by

the syn-btix ligands to generate 1D polymeric [M(btix)2] rings.
The octahedral geometry is completed by two water molecules
in the trans positions. Removal of the coordinated and lattice
water molecules thermally creates a drastic rearrangement in
the structure. The noncoordinating nitrate anions moved to
occupy the vacant coordination sites left by the aqua ligands.
Surprisingly, the syn-btix ligands adopt anti-conformation by
Figure 126. SCSC transformation of a 1D ladder CP, [Pb(ebdc)- rotation around methylene group. Unusually, the coordinating
(MeOH)]·H2O, to 2D MOF, [Pb(ebdc)], by air drying. sphere undergoes drastic changes during this transformation,
which finally yielded a 2D MOF. These two structures are
polymer, ebdc ligand chelates to the Pb(II) center by one supramolecular isomers.
carboxylate group in a κO:κO′ fashion and bridges via the Significant difference in the magnetic coupling interactions
second carboxylate in a μ-(κO:κO′) manner to two different accompany another solid-state interconversion between a 1D
Pb(II) atoms. One MeOH is bonded to Pb(II). Two more CP and 2D MOF due to dehydration and rehydration.706
additional secondary interactions with the oxygen atoms of the Thermogravimetric analysis shows that the coordinated aqua
carboxylates from the adjacent ladders are responsible for the ligand from axial position and the lattice water could be
structural rearrangement when the bonded MeOH is lost. The removed below 200 °C from the green crystals of 1D CP,
primary coordination is generated from these secondary [Cu2(hpdc)(OH)(H2O)4]·H2O (H3hpdc = 2-hydroxypyrimi-
intermolecular weak interactions as shown in Figure 126. dine-4,6-dicarboxylic acid), whereas the aqua ligand from the
A 1D CP [Pb2(8-Quin)2(NO3)2(MeOH)], (8-HQuin = 8- basal plane is lost at >270 °C. The structure of the resultant
hydroxyquinoline) undergoes a structural transformation upon blue 2D MOF [Cu2(hpdc)(OH)(H2O)] formation was
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confirmed by PXRD studies. The single crystals of both 1D CP

and 2D MOF could be obtained using solvent evaporation and
hydrothermal techniques.
A fluorescent zigzag 1D CP [Zn(salpyca)(H 2 O)],
(H2salpyca = 4-hydroxy-3-(((pyridin-2-yl)-methylimino)-
methyl)benzoic acid) packs in the solid state in such a way
that the aqua ligands are complimentarily hydrogen bonded
the adjacent phenolate O atoms (Figure 128).707 Because of

Figure 129. Structural transformations of a 1D linear CP to a 2D

sheet and a 1D ladder CP by grinding and heating processes. Adapted
with permission from ref 710. Copyright 2013 Royal Society of
Chemistry.

surprising that mechanical grinding converts a 2D sheet to a

ladder structure.
4.2.4. 2D to 2D Transformations. A 2D to 2D SCSC
structural transformation takes place in mother liquor. This is
based on a rare heterobimetallic paddlewheel repeating unit
constructed from a macrocyclic ligand, dota (1,4,7,10-
tetraazacyclododecane-1,4,7,10-tetraacetate) (Figure 130).711

Figure 128. Reversible SCSC transformation of 1D CP, [Zn-

(salpyca)(H2O)], to 2D MOF, [Zn(salpyca)], by dehydration and
rehydration. Adapted with permission from ref 707. Copyright 2015
American Chemical Society.

these interactions, the Zn(II) atoms and the neighboring

phenolate O atoms are separated 4.41 Å. When the aqua ligand
is removed thermally, new Zn−O bonds are formed between
the adjacent 1D strands, resulting in the formation of a 2D
MOF, [Zn(salpyca)]. This is a reversible SCSC trans-
formation. Similar thermal dehydration reaction leading to
the formation of 3D MOF from 1D CP has been reported
before.708
Another 1D CP, {Cs2[Co7(citr)4(H2O)13.5]}·15H2O, com- Figure 130. Water-triggered SCSC transformation of 2D MOF,
posed of doubly bridged pair of Co4(citr)4 cubanes forming [ZnCu(dota)(H2O)], to 2D MOF, [Zn0.5Cu1.5(dota)(H2O)]·4H2O.
Adapted with permission from ref 711. Copyright 2016 Royal Society
one edge and with a single bridge serving as the other.709 The
of Chemistry.
ribbons formed side by side. It contains 42 water molecules in
the unit cell. When the crystals are kept at 30 °C for a day,
under dry nitrogen stream on diffractometer, the SCSC First, Cu(II) is incorporated into the cavity of dota and then all
transformation occurs to form a 2D MOF, [Co(H2O)6]- the carboxylates are connected by Zn(II) monomers. This 2D
{Cs2[Co6.5(citr)4(H2O)9]}2·3H2O. After standing at ambient MOF [ZnCu(dota)(H2O)] was synthesized under solvother-
conditions for more than 2 months, the 2D MOF converted to mal conditions at 120 °C after 12 h as sky-blue crystals. If the
back to 1D CP. crystals were left undisturbed in the mother liquor for 72 h,
A linear and photostable 1D CP, [Cu(O2CCF3)2(μ- this is transformed to another 2D MOF, [Zn0.5Cu1.5(dota)-
bpe)(DMF)], was transformed to a photoreactive sheet, (H2O)]·4H2O. In the thermodynamically stable 2D MOF,
[Cu(μ-O 2 CCF 3 ) 2 (μ-bpe)], or a photoreactive ladder, bimetallic paddlewheel repeating units connected to four
[Cu2(μ-O2CCF3)2(O2CCF3)2(μ-bpe)2] CP, by removing the macrocyclic ligands with Cu(II) at its center. However, only
coordinated DMF from the single crystals or the ground two “trans” carboxylates are used in this MOF.
powder, respectively (Figure 129).710 Further, the sheet Suh and coworkers reported a dynamic framework trans-
structure rearranged to a ladder polymer when the desolvated formation involving a porous bilayer 2D MOF on heating to 75
single crystals were ground to powder. These transformations °C for 1.5 h, shrinks its cell volume from 5974.3 to 3877.9 Å3
were monitored by [2 + 2] cycloaddition reaction monitored after the removal of all the pyridine and water guest molecules
by 1H NMR spectroscopy. The TGA studies revealed that the from the lattice. The PXRD shows that this process is
coordinated DMF started leaving from 83.5 °C, which is much reversible when the desolvated product was immersed in a
below its boiling point, 153 °C. This implies that the 1D CP is solution containing water and pyridine in 5 min.408 Retaining
a kinetic product. It is unusual to note that the structural the single crystal with minimal changes in the conformation
changes induced by DMF removal in single crystals and after removal of solvents from the pore of 2D MOFs has also
ground powder gave two different photoproducts. It is rather been noted.712−714
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4.2.5. 2D to 3D Transformations. Unexpected and

unpredicted change in dimensionality from 2D to 3D due to
a drastic change of the building block has also been noted. A
2D MOF [Cu(5-bn)2] (bn = 5-bromonicotinate) with a
layered structure is made up of paddlewheel Cu(O2CCR)4
repeating units in which the apical positions occupied by
pyridyl N atoms (Figure 131).715 When exposed to moist air,

Figure 133. Solvent triggered 2D to 3D MOF structural trans-

formation from [Zn2(mtbpc)(DMF)4]·2DMF·4H2O to [Zn2(mtbpc)-
(H2O)2]·x Solvents. Adapted with permission from ref 718. Copyright
2012 Royal Society of Chemistry.

when the coordinated DMF molecules were exchanged with

water in DCM. The distorted octahedral Zn(II) center has two
Figure 131. Reversible structural interconversion from 2D MOF, chelating carboxylates and two coordinated DMF molecules.
[Cu(5-bn)2], to 3D MOF, [Cu(5-bn)2(H2O)2], showing the color
change due to the coordination geometry of Cu(II).
The Zn(DMF)2 groups are very close to each other between
the interpenetrated layers. When the single crystals are soaked
the paddlewheel building block is converted to monomer in DCM, the coordinated DMF molecules are removed and
repeating units resulted in the formation of a 3D MOF, [Cu(5- triggered rearrangement of bonds. The adjacent carboxylates
bn)2(H2O)2]. Surprisingly, this transformation takes place in stitch bonds between the layers and resulted in the increased
an SCSC fashion, with visible color change from green to blue dimensionality. Because of these structural transformations, the
due to change in the coordination geometry from square- pore volume increased from 28.8% to 41.4%. This is reflected
pyramidal to octahedral where two water molecules are in the increase of hydrogen uptake from 0.3% to 1.75% and the
bonded to Cu(II) in trans manner. The presence of free BET surface area that increased from 177 m2 g−1 to 1170 m2
donor nitrogen atoms closer to the metal ions could be the g−1 at 77 K and 1 atm. The Co(II) analogue also behaves in a
similar manner.
driving force for the structural changes.
A chiral 2D MOF [Ni2(L-tar)2(H2O)2]·3H2O (L-tar = L-
The repeating unit of the 2D MOF [Ce(tci)(H2O)2]·2H2O
tartarate) with extensive hydrogen bonding, on removal of the
(tciH3 = tris(2-carboxyethyl)isocyanurate) consists of a
aqua ligands and guest water molecules at 150 °C overnight
dinuclear Ce(III) center that is bridged by four carboxylates
under vacuum, undergoes structural transformation to a 3D
and further coordinated by two more carboxylate groups and a
structure in an SCSC manner.719 In another example, a
water molecule to complete the 7-coordinate geometry.716 In
paddlewheel based 2D MOF, [Zn2(TBAPy)(H2O)2] (TBAPy
each tci ligand, two carboxylate groups bridge two different
= 1,3,6,8-tetrakis(p-benzoic acid)pyrene), upon desolvation
Ce2(O2C)4 moieties and the third carboxylate group bridges
undergoes a reversible transformation to a 3D MOF as
one of the Ce2(O2C)4 moieties and a third one. All the water
determined by PXRD techniques. The 3D MOF has pts
molecules can be lost, accompanied by a structural change to a
topology with mononuclear Zn(II) building blocks in
3D MOF. Because of the flexibility of the ligand’s arms, the
tetrahedral geometry.720 The 2D to 3D dimensionality changes
−CH2CH2− units can easily move up and down relative to the
is accompanied by change in surface area, adsorption behavior
central tci ring, thus allowing a large structural change, toward p-xylene, and m-xylene and optical properties.
reversibly (Figure 132). A similar 2D MOF with Cu(II), The yellow blocks of two-fold interpenetrated 2D MOF
[Cu2(tci)(OH)(H2O)2]·1.5H2O, is transformed to a 3D [Cd(iba)2] (iba = 4-(1H-imidazol-1-yl)benzoate) with (4,4)
framework reversibly upon the removal of water molecules connectivity were obtained in a hydrothermal reaction at 80 °C
by sliding of the 2D sheets.717 in 6 days (Figure 134),721 while yellow platy crystals of four-
fold interpenetrated 3D MOF [Cd(iba)2(H2O)]·2.5H2O with
dia topology were formed when the single crystals of 2D MOF
were heated in a Teflon-lined stainless steel autoclave at 200
°C for 24 h. Obviously, water in the 3D MOF were picked up
from moist air. In this 2D MOF, the Cd(II) center acts as four

Figure 132. Schematic representation of reversible topochemical

transformation of a 2D to a 3D MOF.

Lin et al. reported a four-fold interpenetrated 2D MOF to

undergo a structural transformation to a 3D structure with dia Figure 134. Change in the coordination sphere during the SCSC
topology by exchanging with solvents (Figure 133).718 The 2D transformation of 2D MOF, [Cd(iba)2], to 3D MOF, [Cd-
MOF, [Zn 2 (mtbpc)(DMF)4]·2DMF·4H2 O (H4mtbpc = (iba)2(H2O)]·2.5H2O, with different interpenetration and dimension-
methanetetra(biphenyl-4-carboxylic acid)), is transformed to ality. Adapted with permission from ref 721. Copyright 2016 Royal
3D MOF [Zn2(mtbpc)(H2O)2]·xSolvents in an SCSC fashion, Society of Chemistry.

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connecting node formed by two chelating carboxylates and two Mn(II) atoms have distorted square-pyramidal geometry by
N atoms from four different iba ligands. Because of the angular three carboxylate oxygen atoms and two nitrogen atoms of the
spacing of the nitrogen donor atom in the imidazole part, the chelating 2,2′-bpy ligands. During the structural trans-
sql lattice is highly corrugated forming two-fold parallel formation, hydration changed the SBUs drastically to a
interpenetration. In the 3D MOF, the Cd(II) center with mononuclear Mn(II) repeating unit in the resultant 1D zigzag
pentagonal bipyramidal geometry due to additional aqua CP, [Mn(1,3-bdc)(2,2′-bpy)(H2O)2]·H2O. The chemical
ligand, it has a tetrahedral node which favors the expected dia composition also changed in this “SCSC” reaction.
topology. The VT-PXRD studies confirmed that this is an This structural transformation involves conversion from one
SCSC reaction. The UV−visible absorption and HOMO− supramolecular isomer to another isomer. When the single
LUMO energy states matched for sensitizing TiO2 and hence, crystals of a non-interpenetrating 2D MOF, [Co(L)2(H2O)2]-
the two MOFs were employed as a co-sensitizer for dye- (NO3)2·2DMF·2H2O (L = 3,5-bis(4-imidazol-1-ylphenyl)-
sensitized solar cells (DSSCs). They have a significant effect on [1,2,4]triazol-4-ylamine), having (4,4) topology, was soaked
the performance of DSSCs, overcoming the deficiency of N719 in 0.1 M formaldehyde in chloroform solution for 5 days, it is
absorption in the region of UV and blue-violet region, structurally transformed to a 1D CP, [Co(L)2(H2O)2](NO3)2·
offsetting competitive visible light absorption of I3− ion and 2DMF·H2O (Figure 135).454 The 1D CP consists of Co2L2
reducing charge recombination of injected electrons.
The following Cd(II) MOFs were synthesized under
different experimental conditions using from 3,4-pyridinedi-
carboxylate (3,4-pydc) and bpee ligands: 2D MOF, [Cd(3,4-
pydc)(bpee)(CH3OH)]·H2O, and 3D MOF, [Cd(3,4-pydc)-
(bpee)0.5(H2O)]·H2O.722 The desolvated 2D MOF undergoes
structural transformation to the 3D structure upon soaking
with water with a loss of half bpee.
4.2.6. Mechanochemical Reactions. Here structural
transformations due to mechanochemical reactions are
described. The 2D MOF, [Mn2(ina)4(H2O)2]·2EtOH (Hina
= isonicotinic acid), is made up of the repeating dimeric units Figure 135. SCSC structural transformation of 2D MOF, [Co-
Mn2(CO2)2, and each Mn(II) center is coordinated to two (L)2(H2O)2](NO3)2·2DMF·2H2O, to 1D CP, [Co(L)2(H2O)2]-
trans pyridyl groups from ina ligand, bridging and mono- (NO3)2·2DMF·H2O, in supramolecular isomerism.
dentate carboxylates and an aqua ligand.723 When NH4NCS is
ground mechanochemically with this 2D MOF, it forms rings due to the angular nature of the ligand. During the
another 2D MOF, (NH4)[Mn(ina)2(NCS)2]·xH2O, with a transformation, there was no change in the crystal morphology,
bilayer net. In this structure solved by synchrotron data, the but the space group has changed from P21/c to C2/c. The 2D
Mn(II) center in octahedral geometry has two pyridyl N MOF containing BF4− anions, the anion can be exchanged
atoms, two O atoms from two monodentate carboxylate with ClO4− and NO3− anions in a SCSC manner.
groups, and two trans NCS groups are projecting normal to the 4.2.8. 3D to 2D Transformations. Sumby et al.
layer. On the other hand, when the bilayer compound was demonstrated a 3D porous MOF, [Ag(dpzm)(DMSO)]ClO4·
heated to 140 °C, the two layers were unzipped with the loss of 0.1(DMSO)·0.9(EtOAc) (dpzm = di-2-pyrazinylmethane),
NH3 to form another 2D MOF, [Mn2(ina)2(Hina)2(NCS)2]. with sodalite topology, to undergo structural transformation
The Mn(II) has tetrahedral geometry resulting from one to a nonporous 2D MOF upon desolvation.725 While being
pyridyl N atom, one thiocyanate N atom, and two O atoms of kept in Paratone oil, the lattice solvents and coordinated
bridging carboxylates. These reactions are neither top- DMSO were removed. This resulted in the collapse of the
ochemical reactions nor SCSC reactions. Nevertheless, the framework to a 2D MOF, [Ag(dpzm)]·ClO4·H2O. The
power of PXRD techniques and Raman spectroscopy have mechanism of such transformation is not clearly understood.
been successfully used to follow the course of the reaction. The 3D MOF contains honeycomb-like 1D channels along the
Such techniques are expected to dominate the literature more c-axis exhibited reversible breathing (expansion and contrac-
and more in the future, as it is not always possible to maintain tion) upon exposure to different solvents.
the single crystals at the end of the solid-state reactions. Five lanthanide MOFs, [Ln2(ANDC)3(DMF)4]·DMF (Ln =
4.2.7. 2D to 1D Transformations. The structural Nd, Gd, Pr, Ce and Sm; ANDC = 9,10-anthracenedicarbox-
rearrangement from a higher dimensional to a lower ylate), with pcu topology were built upon [Ln2(ANDC)3-
dimensional structure can occur due to solvolysis. This is ((DMF)4] repeating units (Figure 136).726 By soaking,
just opposite to the structural transformation discussed above sonicating, or heating under solvothermal or microwave
due to desolvation. There are not many examples reported for conditions with DMA, the 3D MOFs were structurally
the “depolymerization” reactions that are achieved by delinking transformed to nanoplatelets 2D MOFs with hcb topology
the metal−ligand connections from multidentate ligands. with the thickness <100 nm. The single crystals of 2D MOFs
Water plays an important role in these transformations due could also be synthesized by solvothermal methods using
to its ubiquitous presence in solvents and atmosphere. DMA instead of DMF. These Ln-MOFs are potential
A 2D MOF, [Mn3(1,3-bdc)3(2,2′-bpy)2]·2H2O, is trans- upconverting solid-state materials as they are relatively
formed to a 1D zigzag chain upon soaking the single crystals in resistant to dissolution and photobleaching compared to dyes
water for several days.724 The structure of this 2D MOF is in solution.
constructed from trimanganese cluster units. The central A 3-fold interpenetrated 3D framework, [Zn 4 O-
Mn(II) atom adopts octahedral coordination geometry from (L)3(DMF)2]·0.5DMF·H2O (L = 3,3′-dimethoxybiphenyl-
six bridging carboxylate oxygen atoms, whereas the terminal 4,4′-dicarboxylate), has pcu topology similar to the MOF-5
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Figure 136. 3D to 2D transformation of lanthanide MOFs,

[Ln2(ANDC)3(DMF)4]·DMF. Adapted with permission from ref
726. Copyright 2016 American Chemical Society.

structure (Figure 137).727 But, one Zn(II) atom is additionally

coordinated to two DMF molecules in cis mode to have
Figure 138. Reversible structural transformation of 1D CP, [ZnCl2(μ-
bpy)], to 2D MOF, [Zn(μ-Cl)2(μ-bpy)], at high and low temper-
ature.

geometry is bonded to a nitrogen atoms of hep-H ligand, two

bridging chloride and one terminal chloride ions. On heating,
the single crystals of the 1D CP chain to 110 °C for 1.5 h, it is
transformed to a 2D MOF, in which [Hg(μ3-Cl)(hep-H)Cl]2
units are sandwiched between [Hg(μ-Cl)2] chains via μ3-Cl
groups. The 2D MOF transforms back to 1D CP after 3 days at
room temperature. Interestingly, the bromide and iodide
compounds do know show this behavior.
Figure 137. Structural transformation of 3D MOF, [Zn4O-
4.3.2. 0D to 1D and 2D Transformations. The H2bpy
(L)3(DMF)2]·0.5DMF·H2O, to 2D MOF, [Cu2(L)2(DMF)2]·6H2O, are hydrogen bonded to two chlorine atoms of the anions in
via metal ion exchange. Adapted with permission from ref 727. the metal complexes, [H2bpy][MCl4] (M = Pt, Co and Zn), to
Copyright 2014 American Chemical Society. provide hydrogen-bonded networks (Figure 139).731 Dehydro-

octahedral geometry instead of tetrahedral coordination. The

overall connectivity of this MOF has bsn net. This Zn(II)
compound can be converted to 2D MOF with paddlewheel
structure, [Cu2(L)2(DMF)2]·6H2O, by soaking it in DMF/
H2O mixture and heated with Cu(NO3)2·3H2O at 80 °C for 3
days. This is not an SCSC reaction and structure of the known
Cu(II) compound728 was confirmed by comparing with the
PXRD patterns.
4.3. Transformations Induced by Heat Figure 139. Structural transformation of a H-bonded 0D complex to a
1D CP via dehydrochlorination.
The structural transformations described in this section are
attributed to the influence of temperature and the decom-
position of the MOFs in stages. chlorination occurs on heating these complexes in the solid
4.3.1. 1D to 2D Transformations. The zigzag 1D CP, state, leading to the structural conversion. The PXRD patterns
[ZnCl2(μ-bpy)], upon cooling to −143 °C, undergo structural of these already known compounds are matched to confirm
change to a 2D MOF, [Zn(μ-Cl)2(μ-bpy)] (Figure 138).729 these crystalline products. Linear and zigzag 1D CPs are
The distorted tetrahedral Zn(II) center has two bridging bpy respectively formed for Pt(II) and Zn(II) complexes, while
and two terminal chloride ligands and, further, the zigzag Co(II) complex yield a 2D MOF. This is a reversible process
chains are packed one below the other. When the temperature by exposing the CPs to HCl vapors for Co(II) and Zn(II).
is lowered, the chains come close together such that the A discrete metal complex, [Co(NCS)2(2,6-DMPy)4] (2,6-
terminal chloride ligands start bridging the neighboring chains DMPy = 2,6-dimethylpyrazine), has an octahedral Co(II)
to become a 2D MOF. Hence, the Zn(II) centers in the 2D center with a N6 core, when heated to 140−150 °C loses 50%
MOF have distorted octahedral geometry, coordinated by four of the 2,6-DMPy ligands to form a 2D MOF, [Co(NCS)2(2,6-
bridging chloride and two trans-bridging bpy ligands. This DMPy)2] (Figure 140).732 On further heating to 170 °C,
structural conversion is reversible when the temperature is another 50% of 2,6-DMPy ligands to yield a 3D MOF
increased above 87 °C. This reversible structural trans- [Co(NCS)2(2,6-DMPy)]. The course of the reaction was
formation demonstrates the influence of temperature on the followed by TGA and PXRD techniques. The structures were
coordination number and geometry. solved from the powder data. In the 2D MOF, the Co(II)
Lahiri et al. have reported a similar reversible 1D to 2D atoms with a N4S2 core, are bridged by a pair of thiocyanate in
structural transformation by the application of heat.730 Here, in μ-1,3 bridging manner. The dimers are further bonded to two
the 1D CP, [Hg(μ-Cl)2(hep-H)(Cl)] (hep-H = 2-(2- different thiocyanate anions by μ-1,3 bridging to form a layer
hydroxyethyl)pyridine), the Hg(II) center with tetrahedral in the bc-plane. The axial positions of the Co(II) are occupied
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4.4.1. 0D to 1D and 2D Transformations. A 1D CP,

[Zn 2 (L) 2 (bpe) 2 (H 2 O) 2 ] (L = 4,4′-((1,2-phenylenebis-
(methylene))bis(oxy))dibenzoate), has a highly flexible and
bent dicarboxylate ligand responsible for the formation of
helical chain (Figure 141).743 The bpe is acting as a terminal

Figure 140. Stepwise structural transformation of [Co(NCS)2(2,6-

DMPy)4 ] (0D) to [Co(NCS)2 (2,6-DMPy)2 ] (2D) to [Co-
(NCS)2(2,6-DMPy)] (3D) by heating. Adapted with permission
from ref 732. Copyright 2017 American Chemical Society.

Figure 141. Schematic representation for SCSC conversion of a 1D

by 2,6-DMPy ligands. In the 3D MOF, one Co(II) center with CP to a 2D MOF via [2 + 2] photocycloaddition. Adapted with
permission from ref 743. Copyright 2015 Royal Society of Chemistry.
a N6 core has four bridging thiocyanate ligands in the
equatorial plane and two 2,6-DMPy are in trans. The second
ligand and the second N atom is non-coordinated but strongly
Co(II) atom with a S4 core is tetrahedrally coordinated by the
bridging thiocyanate ligands. The 0D complex remains hydrogen bonded to the coordinated water molecule in the
paramagnetic down to 1.8 K while 2D MOF antiferromagnetic third Zn(II) atom in the chains (O7−H7b···N4 and O14−
while ferromagnetic interactions dominate the 3D MOF. The H14b···N3). The bpe ligands from the adjacent helical chains
same group investigated the thermal decomposition reactions are arranged in a head-to-tail manner for a [2 + 2]
of similar CPs with different linear spacers and metal ions cycloaddition reaction. When exposed to UV light, the
along with their changes in magnetic properties.733,734 compound undergoes [2 + 2] photodimerization in an SCSC
The decavanadate (quin)4[H2V10O28] on heating to 230 °C manner to furnish a 2D MOF [Zn(L)(rctt-tpcb)0.5(H2O)]
transforms in the solid-state to a 2D compound (NC7H14)- (rctt-tpcb = tetrakis(4-pyridyl)cyclobutane). The nanospheres
[H2V4O10].735 This is accompanied by a partial reduction of of the 1D CP can be obtained by recrystallization of the
V(V), removal of the amine, and decomposition of the anion. compound from DMSO/alcohol and the nanospheres of 2D
Obviously, this is a thermal decomposition reaction, rather MOF can also be produced by the use of nanospheres of 1D
than a topochemical structural transformation. VT-PXRD and CP for the photocyclodimerization reaction. Compared to the
TGA were used to follow the reaction. This study presented nanospheres of the photoproduct, the nanospheres of 1D CP
the thermal decomposition of a polyoxometalate anion into a display highly selective sensing of Fe3+ ions over mixed metal
2D layered structure. ions via fluorescence quenching. Moreover, the same nano-
4.3.3. 2D to a 3D Structural Transformation. A 2D sphere can adsorb CR (congo red), MB (methylene blue), or
MOF [Zn2(camph)2(py)2]·2EtOH (H2camph = (1R,3S)- RhB (rhodamine B) over MO (methyl orange) rapidly from
(+)-camphoric acid) built from the paddlewheel repeating aqueous solutions.
units are joined by the angular carboxylate, camph. The In an unusual solid-state [2 + 2] photoreaction in a
pyridine groups occupy the apical positions further interact hydrogen-bonded interdigitated 1D CP, [Cd(1,4-bdc)(2F-
with adjacent pyridyl groups in adjacent layers through π···π 4spy)2(H2O)]·2F-4spy, the lattice guest 2F-4spy are nicely
interactions. Both pyridine ligands and EtOH are removed aligned in parallel between the coordinated 2F-4spy ligands to
from this 2D MOF when heated to 150 °C for 12 h. The satisfy the Schmidt’s criteria for [2 + 2] cycloaddition reaction
structure of [Zn(camph)] solved by PXRD reveals that the
(Figure 142).616 Time-dependent photoreactivity studies
Zn(II) centers are linked alternatively in orthogonal directions
by pairs of bridging carboxylates to form a chain, and the
chains are further linked by camphorate ligands resulting in a
non-porous 3D structure. Soaking the crystals of this 3D MOF
in ethanolic solution of pyridine recovers the original 2D MOF
reversibility as indicated by the PXRD studies.736
4.4. Structural Transformations by Photochemical [2 + 2]
Cycloaddition Reactions
Solid-state photochemical [2 + 2] cycloaddition reactions
performed under UV light create new σ-bonds between the
carbon atoms at the expense of intermolecular olefin bond
pairs. This usually results in joining two different coordination
polymeric species, leading to the formation of a new
structure.678−680 Naturally, these photochemical reactions are
accompanied by change in the connectivity and dimension-
ality. During the photoreaction, the structural changes
observed in CPs are quite often associated with the change
of coordination number and geometry around metal center,
change in connectivity, dimensionality and interpenetration, Figure 142. Structural transformation of a 1D CP to a 2D MOF via
and the associated changes in the physical and chemical host−guest [2 + 2] photoreaction. Adapted with permission from ref
properties.737−742 616. Copyright 2014 American Chemical Society.

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provided evidence that the photoreaction proceeds in a

stepwise manner, first between the host−guest ligands followed
by host−host ligands. The end photoproduct of the reaction is
expected to be a 2D layered MOF. But, the recrystallized
photoproduct under solvothermal conditions, the composition
changed to yield [Cd3(1,4-bdc)3(rctt-2F-ppcb)2(DMF)2]·
DMF, which is a 3D pillared layered architecture comprising
a rare bcg net. Figure 144. SCSC structural conversion of 1D CP, [Cd(adc)(4-
The combination of trans-5-styrylpyrimidine (5-Spym) nvp)2(H2O)], to 2D MOF, [Cd(adc)(4-nvp)(rctt-4-pncb)1/2(H2O)],
ligand and [Ag(I)-PPh3]+ cation generated helical chains incorporating enhanced conductivity after dimerization. Adapted with
[(Ph3P)Ag(5-Spym)(X)] with X = NO3−, BF4−, ClO4−, and permission from ref 621. Copyright 2018 American Chemical Society.
CF3CO2− anions.744 The styryl group attached to the
pyrimidine ligand makes these a series of photoreactive 1D olefin bonds, undergoes intramolecular photochemical [2 +
helical CPs. The 5-Spym arms in the adjacent helical chains are 2] cycloaddition reaction statistically in the expected yield of
aligned in a head-to-tail manner. All the helical CPs undergo [2 67% yield via SCSC manner.746 The photo reaction proceeds
+ 2] cycloaddition under UV light, quantitatively leading to the to 100% under UV light, when the single crystals are ground to
formation of 2D MOF (Figure 143). Whereas due to bulky powder. During the mechanical grinding, the coordinated
water molecules are lost and the olefin bonds from the adjacent
ladders reorganized to furnish quantitative photodimerization
which yielded 2D MOF. A similar reaction was described
earlier for another triple-stranded 1D CP, [Pb3(μ-bpe)3(μ-
O2CCF3)2(μ-O2CCH3)2(O2CCF3)2], in the solid state.747
Here, a 2D MOF is formed from a 1D CP by the 50%
photoreaction cleanly (Figure 145).748 In the linear 1D CP,

Figure 143. (a) Schematic representation of structural transformation

from a 1D helical CP to a 2D helical MOF. (b) Structural
transformation of 1D CP, [(Ph3P)Ag(5-Spym)(NO3)], to 2D
MOF, [{(Ph3P)Ag(NO3)}2(rctt-bpcb)], by [2 + 2] dimerization.
Reproduced with permission from ref 744. Copyright 2018 American
Chemical Society. Figure 145. SCSC structural conversion of 1D CP, [Cd(1,3-bdc)(4-
spy)2], to 2D MOF, [Cd(1,3-bdc)(4-spy)(HT-ppcb)0.5], by 50%
photoreaction cleanly. Adapted with permission from ref 748.
nature of the CF3SO3− anion, the olefin group of 5-Spym Copyright 2013 Royal Society of Chemistry.
ligands in the adjacent helical chains normal to each other, and
hence, the single crystals of [(Ph3P)Ag(5-Spym)(CF3SO3)] [Cd(1,3-bdc)(4-spy)2], the two Cd(II) atoms are bonded by
were photostable.745 However, the compound was photo- four 1,3-bdc ligands in which one carboxylate bridges two
reactive when the crystals were ground to powder. The Cd(II) centers and the other carboxylate ligand chelates a
photoreactivity increased with increasing grinding time and Cd(II) center in a plane. The two axial positions of the
quantitative consumption of olefin bonds were observed in 30 octahedral Cd(II) atoms are filled by the 4-spy ligands. The
min of ground sample after 25 h of UV irradiation. Systematic alkene bonds of the 4-spy ligands in the axial positions (i.e., the
studies reveal that anisotropic cell volume expansion occurs by head-to-head pairs) are disoriented and too far apart to undergo
mechanical grinding, which in turn facilitates the concerted a photochemical [2 + 2] cycloaddition reaction. On the
rotation of the photo-inert helical 1D CP, which causes the contrary, the 4-spy ligands from adjacent chains interdigitate in
misaligned arms containing olefin functional groups in the a head-to-tail (HT) fashion. The crystal packing reveals that
neighboring strands to align to undergo [2 + 2] cycloaddition one of the two 4-spy ligands is well aligned with its partner
reaction in 83% yield. from the neighboring strand with a C···C distance of 3.856 Å.
In a double chain ladder-type 1D CP, [Cd(adc)(4- Hence 50% HT photodimerization occurs in an SCSC manner
nvp)2(H2O)] (adc = acetylenedicarboxylate; 4-nvp = 4-(1- UV light to obtain a 2D MOF, [Cd(1,3-bdc)(4-spy)(HT-
naphthylvinyl)pyridine), the olefin pairs from the adjacent 4- ppcb)0.5] (HT-ppcb = 1,3-bis(4′-pyridyl)2,4-bis(phenyl)-
nvp ligands are nicely aligned in a head-to-tail fashion to cyclobutane), has 2D sheet structure. A similar 50% photo-
undergo a photochemical [2 + 2] cycloaddition reaction reaction cleanly in a SCSC manner in 3D MOFs,
(Figure 144).621 This SCSC structural transformation [Cd4(bpe)4(sdb)4]·Solvents, was reported.749
furnished a 2D layer structure [Cd(adc)(4-nvp)(rctt-4- Garai and Kumar described an interesting solid-state
pncb)1/2(H2O)]. Decrease in distance between the intermo- transformation of silver(I) 1D CPs under UV light to undergo
lecular chains as well as π···π stacking interactions between [2 + 2] cycloaddition reaction to form crystalline coordination
pyridine and naphthalene groups going from 1D to 2D polymers of organic polymers (CPOPs) (Figure 146).750 They
structure results in an increase in conductivity and enhanced synthesized four zigzag 1D CPs with AgX (X− = ClO4− and
charge transfer kinetics from 1D to 2D structure. NO3−) and two olefin containing dipyridyl ligands. The
A 1D hydrogen-bonded triple-stranded ladder CP, [Cd- adjacent CPs are aligned parallel in a plane as shown in Figure
(bpe)1.5(NO3)2(H2O)], containing three perfectly aligned 146a, assisted by the intermolecular N−H···O hydrogen
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the single crystals undergo [2 + 2] cycloaddition reaction in an

SCSC manner to form the corresponding cyclobutane ring,
rctt-tpcb. The sorption properties of the desolvated com-
pounds were examined. The bpe containing 2D MOF shows a
hysteresis at the step at 0.06 kPa, which is often observed in
soft crystals with structural changes upon guest accommoda-
tion. In contrast, the rctt-tpcb containing MOF showed normal
isotherms without discontinuous steps.
In the photoreactive 2D MOF, [Cd2(pvb)2(tbdc)(DMF)2]
(H2tbdc = 2,3,5,6-tetrabromobenzene-dicarboxylic acid; pvb =
trans-2(4′-pyridyl)vinylbenzoate), [Cd2(O2C-C)4(py)2] cores
are connected by the tbdc ligands in one direction and a pair of
pvb ligands in the orthogonal direction to form a 2D sheet
structure (Figure 148).752 In this sheet, the pvb ligand pairs are

Figure 146. Formation of CPOPs. (a) Slip-stacked 1D CP chains. (b)

Ag(I) 2D MOFs including (c) the organic polymers. Reproduced
with permission from ref 751. Copyright 2016 Royal Society of
Chemistry.
Figure 148. Reversible structural transformation by the photo-
bonds. The slip-stacked 1D CP chains undergo an SCSC [2 + chemical formation and thermal cleavage of cyclobutane ring.
2] cycloaddition reaction under UV light to furnish the Reproduced with permission from ref 677. Copyright 2013 Royal
CPOPs. In the CPOPs, the organic polymers bonds to the Society of Chemistry.
adjacent CP strands to form the 2D architecture (Figure
146b). This structure can also be viewed as Ag(I) complex of
an organic polymer shown in Figure 146c. The complexation aligned in a head-to-tail fashion, and further, the CC bonds
with Ag(I) resulted in a 2D structure. These are the first in these pvb ligand pair are well aligned and undergo [2 + 2]
examples of single crystalline metal complexes of organo- cycloaddition reaction in the solid state under UV light,
polymeric ligands. yielding the cyclobutane derivative. This photochemical
4.4.2. 2D to 2D Transformations. A 2D to 2D structural reaction appears to facilitate structural transformations from
transformation has been shown to control the CO 2 one 2D structure to another in the solid state. The cyclobutane
sorption properties. Kitagawa synthesized a 2D MOF rings in the photodimerized product can be cleaved thermally
[Zn2(moip)2(bpe)2]·2DMF (moip = 5-methoxy isophthalate). in two different ways to yield a mixture of trans- and cis-isomers
In the dimeric repeating unit, each Zn(II) atom is chelated by of pvb quantitatively as monitored by the 1H NMR
a carboxylate group and bridged by two carboxylate groups spectroscopy. This was one of the earlier attempts to reverse
from two different moip ligands (Figure 147).648 The N atoms the cyclized product in coordination polymers by heating.
of the bpe ligands occupying the axial positions complete the The 2D MOF, [Zn4(OH)2(5-NO2-1,3-bdc)2(5-NO2-1,3-
double-pillared layer structure. Because of the geometric Hbdc)2(ppene)2] (ppene = 4-pyr-poly-2-ene), has an interest-
proximity, the axial bpe ligands are aligned closely in parallel ing (4,4) net (Figure 149).753 The carboxylates and carboxylic
to make this compound photoreactive. Upon UV irradiation, acid bond to the Zn4(OH)2 cluster to form a 1D strand and
the neighboring chains are connected by ppene ligand pairs.
Because of the face-to-face orientations of the ppene ligands,
all the conjugated “butadiene” olefin pairs are nicely aligned,
satisfying Schmidt’s criteria for [2 + 2] cycloaddition
reaction.754 Interestingly, this crystal undergoes single olefin-
pair dimerization to form another 2D structure, [Zn4(OH)2(5-
NO2-1,3-bdc)2(5-NO2-1,3-Hbdc)2(bpbpvcb)], in an SCSC
manner.
The same ppene ligand is successfully used to construct two
more photoreactive 2D MOFs, [Cd(ppene)(1,2-bdc)] and
[Cd(ppene)(Hbtc)]·0.5(ppene) (Figure 150).755 In both
Figure 147. SCSC structural conversion of 2D to 2D MOFs in cases, the dicarboxylate linker forms a ribbon like 1D chains.
[Zn2(moip)2(bpe)2]·2DMF by UV mediated photoreaction. Adapted The carboxylates bound at Cd(II) centers via a chelating/
with permission from ref 648. Copyright 2012 Royal Society of bridging mode μ3-κ2O,O′:κ2O′,O″:κ1O′ for 1,2-bdc and a
Chemistry. chelating bidentate fashion and a bridging μ-κ1O:κ1O′
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Figure 151. 2D to 2D SCSC structural transformation via [2 + 2]

cycloaddition reaction in [Cd2(5F-1,3-bpeb)2(1,3-bdc)2]·0.5DMF·
2H2O. Adapted with permission from ref 742. Copyright 2020 Royal
Society of Chemistry.

from SC-XRD, PXRD, and 1H NMR spectroscopy in solution,

Figure 149. SCSC structural conversion of 2D MOF, [Zn4(OH)2(5- the authors have used solid-state cross-polarization magic angle
NO2-1,3-bdc)2(5-NO2-1,3-Hbdc)2(ppene)2], to another 2D MOF, spinning (CP/MAS) 13C NMR spectroscopy to characterize
[Zn4(OH)2(5-NO2-1,3-bdc)2(5-NO2-1,3-Hbdc)2(bpbpvcb)], via [2 + the photoproducts. Interestingly, this structural transformation
2] cycloaddition reaction. Adapted with permission from ref 753. is reversible and occurs in an SCSC manner when the single
Copyright 2014 Royal Society of Chemistry.
crystals of the photoproduct was heated to 250 °C for 15 h.
Both MOFs are highly photoluminescent and show two
emission bands with maxima occurring around 380 nm when
excited at λ = 319 nm. Among the metal ions investigated, Al3+
ion is able to quench the emission effectively. The photo-
product MOF exhibited much higher sensitivity and selectivity
toward Al3+ ion with the detection limit of 183 ppb.
In the photoreactive 2D MOF [Cd2(adipate)2(bpbde)2]
(bpbde = 1,4-bis(pyridin-4-yl)-1,3-butadiene), the adipate
ligand form the typical dinuclear-based repeating unit by
bridging two Cd(II) atoms and chelating each Cd(II) atom.757
The conformation of the −CH2− chains dictate the formation
of a 1D chain comprising loops or rings similar to the angular
1,3-bdc ligand described above. The axial positions of the
octahedral Cd(II) centers are filled with pyridyl N atoms of the
bpbde ligands results in a 2D MOF. The centroid-to-centroid
Figure 150. SCSC structural conversion of a 2D MOF, [Cd(ppene)- distances (3.79 Å) between the olefin pairs that are aligned in
(1,2-bdc)], to a ladderane 2D MOF, [Cd2(4-tp-3-lad)(1,2-bdc)2], via parallel in the layers are favorable for [2 + 2] cycloaddition
[2 + 2] cycloaddition reaction. Adapted with permission from ref 755. reaction. In fact, 1H-NMR spectroscopy confirms the
Copyright 2017 American Chemical Society. quantitative photoreaction, although single crystals were not
retained after 100% photoconversion. The authors have shown
coordination mode for Hbtc. The ppene ligands are aligned in that the single crystals were retained only up to 52.7%
parallel to generate the 2D MOFs, [Cd2(4-tp-3-lad)(1,2-bdc)2] photochemical reaction, which was achieved in 5 h of UV
and [{Cd2(4-tp-3-lad)(1,3,5-Hbtc)2}·(ppene)], respectively. irradiation (Figure 152). When adipate was replaced by
The face-to-face parallel alignment of the olefin pairs with a pimelate, photoreactive 3D MOF with pcu topology was
separation that are congenial for the double [2 + 2] obtained.
cycloaddition reaction. The photoreaction proceeds under 4.4.3. 2D to 3D Transformations. Three photoreactive
UV light in an SCSC fashion to produce ladderane structure in 2D MOFs, [Zn2(oba)2(X)2]·0.25(X)·xH2O, have been synthe-
which three cyclobutane rings are fused. sized using a bent dicarboxylate, oba (oba = 4,4′-oxy-
1,3-bdc is a very useful ligand to form 1D chains containing dibenzoate) with three different pyridyl (X) derivatives
loops due to the carboxylate ligands directing at 120°. Lang containing olefin functional groups, 4-spy, 4-2npy, and 4-npy
and co-workers have exploited this property to form a (4-2npy = 4-(2′-naphthalen-2-yl)vinyl)pyridine; 4-npy = 4-(2′-
photoreactive 2D MOF with 5F-1,3-bpeb (5-fluoro-1,3-is[2- naphthalen-1-yl)vinyl)pyridine) (Figure 153).758 The building
(4-pyridyl)ethenyl]benzene (Figure 151).756 In this 2D MOF, block comprises two tetrahedral Zn(II) atoms, each Zn(II)
[Cd2(5F-1,3-bpeb)2(1,3-bdc)2]·0.5DMF·2H2O, each Cd(II) center is bridged by two carboxylates from two different oba
in the repeating dimer is linked by three 1,3-bdc via two ligands via μ2-bridging and a unidentate O atom of a oba
bridging and one chelating carboxylate to form a 1D chain ligand and a N atoms of the pyridyl moiety. In the layer formed
made up of loops. Further the axial positions of Cd(II) atoms by Zn2(oba)2, the pyridyl groups are projecting above and
are bonded to 5F-1,3-bpeb ligands to form the 2D MOF. below the layer leading to interdigitation in a head-to-tail
Incidentally, the adjacent 5F-1,3-bpeb ligands within the manner. All the three 2D MOFs undergo [2 + 2] cycloaddition
repeating units are aligned in parallel to undergo [2 + 2] reaction under UV light to the formation of 2-fold inter-
cycloaddition reaction within the 2D MOF. Indeed, this MOF penetrated 3D MOFs with pcu topology. In the case of 4-npy,
undergoes SCSC reaction smoothly under UV light. Apart pedal rotation occurs before the cycloaddition reaction.
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A bilayer 2D MOF [Mn2L2(H2O)2]·3H2O, where H2L is

trans-5-(2-(pyridin-4-yl)vinyl)isophthalic acid, was found to
undergo photodimerization reaction to a 3D structure (Figure
155).759 The octahedral Mn(II) centers are coordinated to two

Figure 152. 2D to 2D SCSC structural transformation in

[Cd2(adipate)2(bpbde)2] showing 52.7% photoreaction. Adapted
with permission from ref 757. Copyright 2014 John Wiley & Sons.

Figure 155. Structural transformation in [Mn2L2(H2O)2]·3H2O from

2D to 3D MOF via interlayer photodimerization.
Figure 153. SCSC structural transformation in [Zn2(oba)2(4-spy)2]·
0.25(4-spy)·H2O from 2D to 3D MOF, [Zn2(oba)2(HT-ppcb)]2·
0.25(4-spy) (HT-ppcb = 1,3-bis(4-pyridyl)-2,4-bis(phenyl)- chelating carboxylate O’s, two syn-anti bridging O’s from two
cyclobutene). Adapted with permission from ref 758. Copyright different ligands, one N from the fourth ligand, and an aqua-
2015 Royal Society of Chemistry. ligand. The bilayer structures are stacked parallel in AAA
fashion. In the intralayers, due to head-to-tail packing of the
One of the distortional supramolecular isomers of the ligands, the distance between the CC bonds were found to
polyrotaxane-based 2D MOFs, [Zn2(bpeb)(sdb)2], was photo- be 4.21 Å, which is slightly longer than Schmidt’s limit.
reactive under UV light in a SCSC manner (Figure 154).584 However, the distance between the olefin pairs present in the
ligands between the adjacent layers, 3.63 Å, is congenial for
photodimerization reaction. This MOF undergoes [2 + 2]
cycloaddition reaction quantitatively in an SCSC manner. This
results in the 2D to 3D structural transformation by the
formation of cyclobutane rings. These MOFs show catalytic
activity of oxidizing phenylmethanol to benzaldehyde.
A bpe derivative, namely HBCbpe (shown in Figure 156)
has been used to make a 2D MOF [Zn(BCbpe)(NO3)2]·
9H2O in which the Zn(II) ion has a distorted tetrahedral
geometry, by bonding to two carboxylate oxygen atoms and
Figure 154. SCSC transformation of a polyrotaxane-like 2-fold
two pyridyl nitrogen atoms from BCbpe ligands.760 The MOF
interpenetrated 2D MOF, [Zn2(bpeb)(sdb)2], to a non-inter-
penetrated 3D MOF by cycloaddition reaction. Adapted with has a (4,4) net with the size of the cavity, 17.52 Å × 17.52 Å.
permission from ref 584. Copyright 2014 John Wiley & Sons. The large voids and corrugation in the 2D layer facilitate 2-fold
interpenetration, leading to a 2-fold interlocked bilayer. The
bilayers further stack together in the −AB− fashion through
The Zn2(sdb)2 form a ring, and the long bpeb acts as rod to the slipped π-stacking interaction between pyridinium and
form this doubly polycatenated 2D MOF. The olefin bonds of pyridine moieties of the adjacent molecules and between two
the bpeb ligands between the neighboring interpenetrating benzene rings, and this generated a 1D channel with a hexagon
structures were aligned in parallel and undergo [2 + 2] window size of about 23.24 Å × 21.16 Å. The closest distance
cycloaddition reaction. The two-fold entangled (4,4) net between the adjacent olefinic double bonds, 3.97 Å, suggests
structure is transformed under UV light to a non-inter- that this 2D MOF could be photoreactive. However, UV
penetrated structure in an SCSC manner due to the formation irradiation experiments indicate only 60% photoconversion.
of cyclobutane rings between the adjacent CC bonds. Both of the 2D MOF solids were tested for the gas-
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Figure 157. Unusual hetero-cross-coupling between 3F-spy and

fumarate along with the normal photocycloaddition reaction between
the 3F-spy pairs are shown. Adapted with permission from ref 761.
Copyright 2018 American Chemical Society.

Figure 156. Structural transformation in [Zn(BCbpe)(NO3)2]·9H2O

from 2D to 3D MOF via photodimerization in −AB− layered fashion.
Adapted with permission from ref 760. Copyright 2017 Royal Society
of Chemistry.

chromatographic separation of water, methanol, and ethanol as Figure 158. (a) Chemical diagram of the isotactic polymer, poly-
bppcb. Adapted with permission from ref 766. Copyright 2015 John
stationary phase. The 2D solid with a partially modified
Wiley & Sons. (b) SCSC structural conversion of 2D to 3D
cyclobutane ring shows remarkable separation of ethanol from polyrotaxane-MOFs via photo-polymerization. Reproduced with
water. permission from ref 762. Copyright 2014 Royal Society of Chemistry.
In this rare example, only 25% of the olefin pairs were found
to meet the Schmidt’s criteria and undergo [2 + 2] nicely aligned to satisfy the Schmidt’s criteria for photo-
cycloaddition reaction cleanly in an SCSC manner. The 2D reaction.754 The structural transformation readily occurs
MOF, [Zn2(fumarate)2(H2O)2(2F-4spy)4], has a fes net between the well-aligned alternate bpeb ligands under UV
topology formed by Zn(fumarate) and the axial positions of light yielding another 3D polyrotaxane MOF in an SCSC
the octahedral Zn(II) centers are occupied by the twisted 2F- manner. The photoproduct contains an unusual isotactic
4spy ligands.761 The intramolecular 2F-4spy ligands are not organic polymer763−765 made up of cyclobutane rings, namely,
close enough to undergo cycloaddition reaction within the poly-1,3-(4,4′-bipyridyl)-2-phenylcyclobutane (poly-bppcb).
sheet. However, the olefin bonds from one-fourth of the 2F- The 2D MOF [Zn2(1,4-bdc)2(2F-4spy)2] is built from the
4spy ligands from the adjacent layers separated by 3.907 Å are paddlewheel building block, and the axial positions are
found to be photoreactive. On UV exposure, the 2D MOF occupied by the monodentate 2F-4spy ligands (Figure
undergoes [2 + 2] cycloaddition reaction in an SCSC manner 159).647 The overall structure has a (4,4) net, and the 2D
to form a 3D structure with dmc topology.
In contrast, the corresponding 3F-4spy ligand furnished
another photoreactive 2D MOF, [Zn2(fumarate)2(3F-4spy)2],
based on paddlewheel building block.761 On exposure to UV
light, this MOF forms a cyclobutane ring arising from the
hetero-cross-coupling of 3F-4spy and fumarate in addition to
the expected cyclobutane ring, rctt-3Fppcb (rctt-3F-ppcb = 1,3-
bis(4′-pyridyl)-2,4-bis(3′-fluorophenyl) cyclobutane) by the [2
+ 2] photocycloaddition reaction of 3F-4spy pairs aligned in a
head-to-tail fashion (Figure 157). The photoreaction is
incomplete, and this is not an SCSC reaction. However, Figure 159. Schematic diagram depicting the SCSC transformation of
solution-like behavior of a solid-state reaction observed here a 2D sheet to a pillared-layer 3D MOF by [2 + 2] cycloaddition
seems to be very unusual. reaction. Adapted with permission from ref 647. Copyright 2015 John
A conjugated diene ligand, bpeb has been successfully used Wiley & Sons.
to carry out the photopolymerization using the well-known [2
+ 2] cycloaddition reaction inside a polyrotaxane-based 2D sheets are interdigitated by four 2F-4spy ligands from four
MOF (Figure 158).762 In the 2D MOF, [Cd(bpeb)(sdb)]· different sheets above and below the plane. The CC bonds
DMA, two Cd(II) atoms and two sdb ligands for a ring. Each of the 2F-4spy ligands from first and fourth layers are packed in
ring is further linked by four bpeb ligands. Because of large size parallel but in head-to-tail fashion, which are suitable for the [2
of the Cd2(sdb)2 ring and long bpeb ligand, it forms rotaxane + 2] cycloaddition reaction. The 2D MOF underwent
type entanglement with 2-fold interpenetration. The alternate photoreaction under UV light in a SCSC manner and resulted
bpeb ligands in the [Cd(bpeb)] zigzag chains pack in a slip- in the formation of triply interpenetrated pillared-layer 3D
stacked manner in a plane such that the olefin bond pairs are MOF. This is a general method of making 3-fold inter-
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penetrated MOFs using cyclobutane-based pillar ligands with

many other dicarboxylate spacer ligands such as 4-carbox-
ycinnamate (cca) and 2,6-naphthalene dicarboxylate (nda).
Other 4-spy derivatives have been used for this purpose.646
A similar photoreactive 2D MOF was synthesized with 3F-
4spy ligand by Lang and co-workers and investigated for the
SCSC photoconversion to the 3D structure.767 The long thin
needles of [Zn2(1,4-bdc)2(3F-4spy)2] were shown to undergo
irreversible photomechanical deformation under UV light by
the [2 + 2] cycloaddition reaction. This deformation includes
bending, helical, and splitting behavior. Furthermore, compo-
site membrane thin films made by this MOF and poly(vinyl
alcohol) (PVA) show macroscopic scale photodeformation,
thus giving hope to the developments of photoactuators. Lang
and co-workers have further used 3-methylstyrylpyridine
(3Me-4spy) to make photoreactive 2D MOFs similar to the
4-spy derivatives used by Vittal and co-workers. Furthermore,
the thermal expansion and photoinduced nonlinear contraction
of these MOFs were also investigated.768
A highly corrugated 2D MOF was synthesized with alkyl
chain based dicarboxylate spacer ligand (Figure 160).769 The

Figure 161. An SCO modulated SCSC structural conversion in 2D

MOF [Fe(4-spy)2{Ag(CN)2}2] via [2 + 2] cycloaddition reaction.
Adapted with permission from ref 770. Copyright 2019 Royal Society
of Chemistry.

MOF, while the SCO transition temperature is well below this

temperature for the photoreacted 3D MOF.
4.4.4. Stepwise Formation of a MOF from 1D CP. Here
is an unusual structural transformation of a 1D CP converted
to 3D MOF in two steps. The first step involves dehydration
leading to the formation of a 2D MOF, which is converted to a
Figure 160. SCSC transformation in [Ni(adipate)(4-spy)2(H2O)2] pillared-layer 3D MOF by [2 + 2] cycloaddition reaction
from 2D to 3D MOF via photodimerization. Adapted with permission (Figure 162).771 Both analytical and spectroscopic tools have
from ref 769. Copyright 2017 Royal Society of Chemistry. been used to establish this stepwise structural transformation.
The hydrogen-bonded 1D CP, [Cd(1,4-bdc)(4-spy)2(H2O)]·
2H2O·2DMF, is a photo-inert kinetic product. The TGA
shows the loss of coordinated and lattice water in the
2D layers in [Ni(adipate)(4-spy)2(H2O)2], the Ni(II) atoms temperature range 50−85 °C followed by the removal of
are coordinated by one water molecule and three oxygen atoms guest DMF by 120 °C. When the aqua ligands are lost along
of carboxylate anions from three different adipate ligands to with guest molecules, the Cd(II) atom forms a bond with the
generate the 2D layered structure. The adjacent layers are O atoms from the carboxylate of the 1,4-bdc ligand in the
interdigitated in such a way that a pair of olefin bonds of one of adjacent 1D strand. This is followed by the formation of a
the two 4-spy ligands is nicely aligned in head-to-tail manner to Cd2O2 ring. In the newly formed layer structure of Cd2(1,4-
undergo [2 + 2] cycloaddition reaction. Upon UV irradiation, bdc)2, the 4-spy ligands are axially coordinated. As a result, the
this 2D MOF undergoes photoreaction in an SCSC manner to 4-spy are drawn closer in a head-to-tail manner to be
provide a 3D structure. photoreactive. The 2D layered MOF, [Cd2(1,4-bdc)2(4-
A photoreactive 4-styrylpyridine was incorporated into the spy)4)], is transformed to a 3D structure by solid-state
spin-crossover (SCO) 2D framework, and the SCO behavior photochemical [2 + 2] cycloaddition reaction between 4-spy
was modulated by the [2 + 2] cycloaddition reaction (Figure ligand pairs from the adjacent layers. The NOESY NMR
161).770 The orange block single crystals of the 2D framework, studies showed the formation of cyclobutane ring from the
[Fe(4-spy)2{Ag(CN)2}2], undergo quantitative SCSC photo- head-to-tail arrangement of 4-spy ligands, which in turn
dimerization reaction. The metallo-ligand [Ag(CN)2]− is a supports the formation of a 3D pillared-layer structure. Similar
linear spacer ligand forming a layer with Fe(II). The 4-spy coordination environments have been found from the XAFS
groups are disposed above and below the layers. Similar to the data for 2D and 3D structures in the absence of SC-XRD.
examples described above, interdigitation occurs and hence the Overall, this is a stepwise solid-state structural transformation
photoproduct is a two-fold interpenetrated 3D framework with from 1D hydrogen-bonded CP to a 2D layered MOF by
pcu topology. The SCO behavior was observed in the desolvation and to a 3D pillared layer MOF by photochemical
temperature range of 212−215 K for the photoreactive 2D transformations.
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Figure 163. Reversible rotation of phenyl rings to open and close the
pore. Adapted with permission from ref 775. Copyright 2014
American Chemical Society.

4.6. Post Synthetic Modifications (PSMs) and Reactions

Post-synthetic modification (PSM) is an approach to function-
alize the backbone of the ligands in MOFs after synthesized.
Using this approach topologically identical, but functionally
diverse MOFs can be obtained in the solid state.777−782 There
is no topological change or structural transformation expected
during this process. In this context, metal ions or metal clusters
in the 2D MOFs can be exchanged in an SCSC manner.783−785
However, these metal ion exchange reactions are out of the
scope of this review.
Figure 162. Schematic representation of step-by-step structural
transformation from 1D CP to 2D MOF to 3D MOF by desolvation 4.6.1. Solvent-Assisted Linker Exchange (SALE)
and [2 + 2] cycloaddition reaction. Adapted with permission from ref Reactions. The solvent-assisted linker exchange (SALE)
771. Copyright 2015 John Wiley & Sons. involves a heterogeneous reaction of the MOF crystals with
a concentrated solution of linkers. In this way, SALE reaction
4.5. Structural Distortions due to Motion of Groups in the can be used for bridging-linker replacement or post-synthetic
Spacer Ligands exchange to form a new MOF (Figure 164). Additionally, a 2D
MOF can be transformed into a 3D MOF by linker insertion
Pedal-like motion of olefin bonds in organic molecules with
between the layers using this simple strategy.786,787
phenyl or pyridyl or other aromatic substituents are often
observed in this solid state.772 As a consequence, this motion
causes disorder in crystal structure due to concomitant
conformational interconversion.773 This pedal-like motion
has been responsible for various unusual behaviors like
unexpected photodimerization between crisscross olefin pairs,
photoisomerization, photochromism, etc.
Apart from organic solids and metal complexes, 2D MOFs Figure 164. Schematic representation of the formation of different
were also reported to exhibit pedal motion of ligands layered structures by SALE method. Reproduced with permission
containing unsaturated bonds. For example, a 2D MOF, from ref 787. Copyright 2015 John Wiley & Sons.
[Cd(azim)2(DMF)2](ClO4)2·(2DMF) (azim = bis(4-imida-
zol-1-yl-phenyl)diazene), exhibits pedal motion of azo groups
triggered by both heat and removal of guest molecules.774
Interestingly, this can be restored by soaking the single crystals The 2D sheets usually comprised paddlewheel building
in DMF. The pedal motions have also been observed by blocks with carboxylate spacer ligands. The linkers are the
solvent exchange in an SCSC manner. dipyridyl spacer ligands and the resultant 3D MOF contains
Rotation of phenyl rings has also been noted in 2D MOFs. A pillared-layers. Farha et al. have reviewed this literature,786,787
semirigid ligand, L (L = 4,4′-(1,4-(xylene)-diyl)bis(1,2,4- and hence this will not be covered extensively and only a few
triazole)), binds to Cu(I) and form a 2D MOF, [Cu(L)- recent literatures are highlighted here.
(ClO4)]·DMF·H2O.775 The structure is made up of 1D When the single crystals of a 2D MOF [Cd3(BTB)2-
nanotubes formed by the syn conformation of the ligand and (DEF)4]·DEF (BTB = benzene-1,3,5-tribenzoate) immersed in
further fused together by the Cu(I) metal atoms. The phenyl a CHCl3 solution of bpe yields an interpenetrated 3D MOF,
ring between the triazole groups can rotate between parallel [Cd3(BTB)2(bpe)(H2O)2]·(bpe) (Figure 165).788 The 2D
and perpendicular positions in a synchronized manner as a MOF comprises three linear trinuclear Cd(II) node in which
function of guest solvent. These rotations of the phenyl rings the central Cd(II) atom is bridged by four carboxylate groups
open and close the 1D nanotubes as confirmed by PXRD and two DEF ligands, while the terminal Cd(II) atoms have a
techniques and 13C CP-MAS NMR spectroscopy (Figure 163). chelate carboxylate group and a DEF ligand. The DEF ligands
Rotation of bpy ligand was observed in solid-solutions of are projecting out of the 2D layers, which enable the SALE
[Zn(5-nitrophthalate) x (5-methoxyisophthalate) ( 1 − x ) - reaction to occur to yield the 3D MOF. The reversible SALE
(deuterated-bpy)]·DMF·MeOH by the solid-state 2H-NMR reactions can take place when the 3D MOF is immersed in
spectroscopy. The changes in local environment around the DEF, via two intermediates with partially occupied mixed pillar
molecular motors by the variation of the dicarboxylate provides ligands [Cd3(BTB)2(bpe)1.8(DEF)0.9(H2O)0.8] in 100 seconds
control of the rotation frequency without varying the and [Cd3(BTB)2(bpe)2(DEF)2] after 1 h, before finally
temperature.776 shuttling back to 2D MOF after 6 h. Similar SALE reactions
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According to Kitagawa, the flexible MOFs belong to the third-

generation crystals driven by internal guest-induced stress have
unique structural softness and reversible structural retention
properties.672 These soft and dynamic nature of the frame-
works have great impact on the porosity and host−guest
interactions, such as “gate opening” and guest induced pore
expansion. These provide unique adsorption profiles and
opportunities for guest sorption and separation.792 In 1997,
Mori et al. have shown that the N2, Ar, O2, and Xe gases can be
included into the pores of a 2D MOF [Cu2(1,4-bdc)4(H2O)2]
at liquid nitrogen temperature.793 Currently, the fabrication of
MOFs into 2D nanosheets is equally gaining in importance for
Figure 165. Reversible SALE structural conversion of 2D MOF, their upgraded performance in sorption and separation of gas
[Cd3(BTB)2(DEF)4]·DEF, to 3D MOF, [Cd3(BTB)2(bpe)(H2O)2]· and guest molecules. Thus, this section has been further
(bpe). Adapted with permission from ref 788. Copyright 2020 Royal divided into subsections based on the (i) gate-opening
Society of Chemistry. property, (ii) breathing property, (iii) pore functionalization,
(iv) nanosheet fabrication, and (v) structural transformation in
with a series of linear and bent spacer pillar ligands have been 2D MOFs.
explored with the same 2D MOF by the same group.783−785 5.1.1. Gate Opening Materials in Interdigitated
4.6.2. Ligand Replacement/Substitution Reactions. Structures. Kitagawa et al. synthesized an interdigitated 2D
Taller pillar ligands in the pillared-layer 2D sheet structures MOF, [Zn2(ip)2(bpy)2]·DMF, in which the double-chain
can be substituted by the shorter pillars to achieve 2D to 2D formed by [Zn2(ip)2] moieties are linked by bpy ligands via
MOF transformation as they can diffuse through the channels axial positions of the Zn(II) atoms.637 The adjacent layers are
(Figure 166). Further, the insertion of pillar ligands between slip stacked and interdigitated by the protruding hydrophobic
2D bilayers has also been achieved successfully to construct the phenyl rings. Type-I adsorption isotherm of CO2 at 195 K was
pillared-bilayer MOFs.789−791 observed on the guest-free 2D MOF, and the adsorbed amount
of CO2 corresponds to two CO2 molecules. Further, the
sorption studies showed selective MeOH sorption compared
to H2O with type-V adsorption profile with weak “adsorbent−
adsorbate” interactions from the hydrophobic framework via
dynamic structural transformation. The sorption properties of
this MOF has been modified by changing the size, shape, and
dimensionality of the nanocrystals by using inverse micro-
emulsion (oil in water) technique.794 Very recently, four
interdigitated 2D MOFs, [Zn2(ip)2(tdih)2], [Zn2(NH2ip)2-
(tdih)2], [Cd2(ip)2(tdih)2], and [Cd2(NH2ip)2(tdih)2] (tdih =
terephthalaldehyde di-isonicotinoylhydrazone), have been also
reported in which amino-based frameworks displayed rever-
sible gated CO2 adsorption at 195 K with higher uptake
Figure 166. Schematic representation of ligand substitution in 2D capacity compared to without amino-substituted ones.795
layers leading to the formation of another 2D sheet. Another flexible layer structure, [Cd(bpndc)(bpy)] (bpndc
= benzophenone-4,4′-dicarboxylate), show a large difference in
gate-opening pressure between O2, Ar, and N2 (Figure 167).796
5. PROPERTIES AND APPLICATIONS The gate-opening characteristics have been quantified as O2 >
The importance of a material depends on versatility and the N2 > Ar, which is very similar to the boiling point of the
impact that material can make on the future technological respective gases. Further analysis showed that these sorptions
advancements. The ultimate driving force for any material is follow anti-Arrhenius behavior due to clatharation reactions of
towards achieving a range of useful properties as well as an organic host.
applications that can be targeted via design. Among different
materials, MOFs exhibit a number of properties and
applications mainly through modular design. Because of
inherent layered structures, 2D MOFs are suitable for making
very thin nanosheets desirable for various applica-
tions.6,7,9−14,16,17 In this section, some of the properties and
applications of 2D MOFs in their various forms including
nanosheets are discussed.
5.1. Sorption, Storage, and Separation of Guest Molecules
3D frameworks are expected to have better thermal stability
and permanent porosity than 2D MOFs for gas sorption and Figure 167. Gate opening of the 2D MOF due to adsorption at low
storage properties, however, in 2D layers, the porosity can be pressure. Reproduced with permission from ref 796. Copyright 2008
made accessible by the expansion of the interlayer distances. John Wiley & Sons.

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The length of the linker and increasing the aromatic group

also plays a key role in sorption properties which has been
established through [Cu(H2dhbpc)2(bpy)] (H2dhbpc = 4,4′-
dihydroxybiphenyl-3-carboxylic acid)797 and [Zn(2,7-ndc)-
(bpy)] (2,7-ndc = 2,7-naphthalene dicarboxylate).640 These
materials have shown significant enhancement in the selectivity
of CO2 compared to CH4 and other gases. This is mainly due
to the change in the pore and window size and interaction of
guest molecules with the aromatic moieties of the linker.
Similarly, change in the length of the neutral linker and its
influence on the selectivity of gas and solvent molecules have
also been established.641,644,798 Even the combinational linkers
in the same framework or the solid-solution studies, usage of
redox metals,799 and its role of gas separation properties have Figure 168. Change of volume of before CO2 adsorption (a) and after
also been established.800 CO2 adsorption at 273 K (b, 6.66 kPa; c, 13.3 kPa; d, 26.7 kPa; e, 34.7
5.1.2. Sliding and Swelling of the 2D Framework. kPa; f, 45.3 kPa; g, 101 kPa) in [Cu(BF4)2(bpy)2]. (h) Schematic
Breathing and sliding of 2D layers is another important representation of swelling of the 2D layered MOFs during the gas
mechanism for gas sorption studies of 2D MOFs. Because sorption. Adapted with permission from ref 696. Copyright 2006
most of the layers are known to have significant open space American Chemical Society.
due to the bridging of the metal nodes with rigid and long
organic linkers. However, because of various modes of of Ni-MOFs, [Ni2(bpy)3(NO3)4], at 77 K.810 In this
arrangement of these layers (most often ABAB or ABCABC compound, bpy bonded to Ni(II) and formed T-shaped
manner or other) lead to the inaccessibility of these pores. nodes, which further coordinated in different passion and
Sliding or swelling of the layers is one of the important and produced different polymeric as well as polymorphic structures
simplest mechanism to access these channels or pores, and it is with 2D interdigitated along with parallel stacked 1D chains.
also one of the energy efficient mechanism. Among, 2D interdigitated structures showed cavity dimensions
Kaneko’s group has presented a quasi-square grid 2D layered up to 8.3 Å and showed H2 uptake up to 3.265 mmol/g at 1
stacking structure, [Cu(BF4)2(bpy)2], with dimensions 1.13 × bar and 196 K. Large hysteresis at low pressures during H2
1.15 nm2 that are separated by 0.46 nm. Further, the layers sorption has been observed due to the strong interaction of H2
stacked in ABAB manner and lead the structure with no pores with the framework. This is one of the first reports which
for gas sorption studies. The CO2 sorption studies at 273 K showed strong hysteretic gas sorption behavior, especially with
presented S-shaped sorption behavior. This is due to the nonpolar guest molecules like H2. Later, various other groups
sliding of the stacked layers to create channels for the free have reported similar H2 sorption with different framework
movement of CO2 gas molecules between the layers until the materials.374,811−816
critical pressure. After this critical pressure, the compound Later, Maji and co-workers presented sliding of 2D layered
showed strong adsorption of CO2 gas with rectangular-shaped MOF, [Cu2(cis-chdc)2(bpe)]·H2O (chdcH2 = 1,4-cyclohex-
hysteresis, follows the gate-opening adsorption.696 After anedicarboxylic acid), where the layers are arranged in ABAB
significant increase in the pressure, especially after the critical manner.817 Because of this ABAB arrangement, the porosity of
pressure, the interlayer distance has been increased to 0.68 nm, the framework and channels are not easy to access. Sliding of
which almost corresponds to the 49% increase of the interlayer the layers is the basic mechanism to access the pores of these
distance, hence to cause adsorption of more molecules rapidly frameworks. Such a sliding has been studied, and its role of
and showed sharp rise in the adsorption behavior. Meanwhile, sorption properties of gases and solvents have been established
this increase in interlayer distance also reflected in the through the change in unit cell during activation as well as
expansion or incremental volume by the powders as shown solvent sorption of the materials and X-ray diffraction (Figure
in Figure 168. In addition to CO2, CH4 also showed similar 170).
hysteresis, however, because of the less polar/quadrupolar Nakamura et al. presented an interesting 2D MOF,
nature of the CH4, the gate-opening pressure is significantly [Cu(PF6)2(bpy)2], where the PF6− anions can interact with
higher than the CO2.801,802 the polarizable molecules such as CO2 moderately and cause
Swelling of 2D framework material has also been realized by selective adsorption.818 This material also presented the
changing the counter anion from BF4− to OTf− anion to yield stepwise adsorption of various gases due to the microfilling
[Cu(OTf)2(bpy)2] (Figure 169). Because of swelling of this of the voids in the 2D MOFs followed by the gate-opening
framework, double the amount of N2 adsorption was achieved phenomenon (Figure 171). This work highlights the
in two steps with a hysteresis.803 The second step may be potentiality of this material for commercial applications due
attributed to the increase of the pore volume by expansion of to the easy recyclability and regeneration of materials with no
the interlayer regions. Similar examples with dynamic nature of or low energy of activation.
the framework and hysteresis with various guest molecules has 5.1.3. Role of Pore Functionalization. Along with the
highlighted the importance and the role of “guest−framework” dynamic nature, functionalization can be another important
interactions and the role of swelling in selective sorption strategy in the field of MOFs, which was well established in
studies.804−806 In a few cases, the crystallinity of the framework various 3D MOFs for the separation of guest molecules.819−821
also lost and might be due to the loss of long-range order This section will provide similar strategies that have been
during this dynamic behavior.807−809 employed in 2D MOFs. Among them, most prominent ones
The research groups of Rosseinsky and Thomas presented are (i) open metal site or coordinative unsaturated site and (ii)
an interesting hysteretic sorption of H2 using two polymorphs introduction of functional sites or groups.
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Figure 169. Change in interlayer distances during the guest molecule adsorption. Reproduced with permission from ref 803. Copyright 2007
American Chemical Society.

Agarwal and co-workers presented a 2D framework,

[Ni3(TBIB)2(btc)2(H2O)6]·5C2H5OH·9H2O (TBIB = 1,3,5-
tri(1H-benzo[d]imidazol-1-yl)benzene), where the 2D layers
are stacked in ABAB manner through strong intermolecular H-
bonding interactions.822 The presence of open Ni(II) sites and
functional organic groups (uncoordinated O atom) lead to a
selective separation of CO2 over CH4, Ar, N2, and H2. The
sorption studies showed type-I sorption profile with 100 cc/g
of CO2 sorption at 195 K, with BET surface area of 297 m2/g.
However, no uptake of N2 and H2 has been observed, suggests
the strong interlayer interaction in the material. In other words,
the interaction between the gas molecules and the framework
is not enough to access these pores. However, polar CO2 could
interact strongly with both the open metal sites and the
uncoordinated O atoms of btc linker and show significant and
selective CO2 adsorption.823
Pore functionality is considered to be one of the best
strategies to enhance the selectivity.824 Hong and co-workers
successfully implemented the pore functionalization in 2D
MOF, [Zn 3 (TCPB) 2 (H 2 O) 2 ] (H 3 TCPB = 1,3,5-tri(4-
carboxyphenoxy)benzene), using ether groups from the
linker.825 Because of the packing behavior of 2D layers in
ABAB fashion, a 1D channel has been formed with the
effective pore size of 4.3 × 4.3 Å2. This channel is exposed to
coordinated water molecules along with ether oxygen atoms
Figure 170. (a) Schematic view showing the sliding of the layers. (b)
and facilitate the polar pore structure. This polar pore helped
Adsorption of various guest molecules. Adapted with permission from in the selective sorption of highly polarizable gas molecules,
ref 817. Copyright 2009 American Chemical Society. such as CO2. Because of these polar channels, the materials did
not show any N2 sorption, although the channel sizes are larger
than the kinetic diameter of N2. This has been utilized for the
selective sorption of CO2/N2 with selectivity 35.7, CO2/CH4 is
2.2, CO2/CO is 24.9, and CO2/H2 is 245.8 at 298 K (Figure
172).
In addition to the oxy functional groups, N-based or amine
functionalization is also known to enhance the selectivity of
polar gases and guest molecules. Hg- and Cu-based 2D MOFs,
[Hg(4-pyf)2]·2(THF) and syn-[Cu4(4-pyf)4]·2EtOH (4-pyf =
N,N′-bis(pyridine-4-yl)formamidine), which showed selective
adsorption of CO2 over other gases mainly due to the amine
groups in the linker. In addition, among these, Cu-system has
less solvent accessible volume, presented higher Qst values for
CO2 sorption. This suggests the stronger interaction of gas
molecules with the framework has been observed due to the
lower solvent accessible volume.826
Another N-based functionalization has been established by
Yang et al.827 through [Zn3(μ3-OH)(tzba)2(bpy)(H2O)]
(H2tzba = 4-(1H-tetrazol-5-yl) benzoic acid), with a linker
Figure 171. (a) Solid-state structure and (b) packing of the 2D MOF. consisting of both carboxyl and tetrazolyl groups. The 1D
(c) Stepwise adsorption of various gases. Adapted with permission rectangular channels as large as 6.0 × 5.7 Å 2 with
from ref 818. Copyright 2013 American Chemical Society. functionalization of N and O groups. This helped in the
selective sorption of CO2 with Qst up to 40.9 kJ/mol. These
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Figure 172. (a) Structure and nature of pore in [Zn3(TCPB)2(H2O)2 and (b) the sorption plots at 298 K. Adapted with permission from ref 825.
Copyright 2013 Royal Society of Chemistry.

polar interactions between the CO2 and the framework has

even been established through GCMC simulations.
Banerjee and co-workers presented an interesting and
systematic study to understand the role of coordinated anions
in an isostructural layered MOF, [M(dmpt)2(X)2], (M =
Cd(II), X = NO3−, Br−, I−; M = Co(II), X = Cl−; dmpt = 4′-
(3,4-dimethoxyphenyl)-4,2′:6′,4″-terpyridine).828 This 2D
layer structure consists of sql topology, where the layers are
stacked through van der Waals interactions in ABAB pattern
with 1D channels along the c-axis. Because of the flexibility of
the framework and the presence of diverse coordinated anions
with different size, the channel size is altered in all the four
frameworks, although all these materials are isostructural in
nature (Figure 173a−d). The coordinated counter anions are
pointed towards the pore and helped to study their interaction
with the gas molecules specifically CO2. In the case of NO3−
substituent, compound showed the highest CO2 sorption
followed by Br−, I−, and Cl− (Figure 173e). This is due to the
strong polarizing ability of the NO3− followed by size of the
pore. Hence, this study has established the selectivity of the
CO2 sorption through the incorporation of polarizing group as
the primary parameter followed by the porosity or the solvent
accessible volume.
In addition to the open metal sites, polar functionaliza-
tion,158,353,829−841 nonpolar substituents is another direction to
modify the selectivity.842−844 Similarly, sorption of various
solvent molecules including water molecules713,845,846 was also
achieved through these functionalizations.760,847−851
Incorporation of co-linkers or supporting linkers also has
been established to instill the hydrophobic nature of the pore Figure 173. (a−d) Solid-state structures of [M(dmpt)2(X)2] and (e)
their CO2 sorption plots. Adapted with permission from ref 828.
and the framework. Pavlishchuk and co-workers presented
Copyright 2014 Royal Society of Chemistry.
pivalates substitution in the 2D MOFs, [Fe 2 M(O)-
(piv) 6 (bpy) 1.5 ]·2DMF (M = Ni(II), Co(II); piv =
(CH3)3CCO2−) with tri-metallic SBU to obtain honeycomb
1D channels has been established through N2 sorption along
framework (Figure 174).852,853 The channels of these honey-
with H2 at 77 K.
comb structures are exposed to the coordinated co-ligand In addition to the selective sorption of various guest
(pivalate) moieties with significant hydrophobic nature. Thus, molecules, sorption of volatile iodine has also been reported by
these materials expected to show selective sorption behavior. using 2D MOFs. Proserpio et al. presented the sql nets
In line with the designed strategy, the compound showed constructed from CuI, namely, [Cu2(μ3-I)2(μ-bpb)], [Cu(μ2-
selective adsorption of linear alkyl hydrocarbons with I)(μ-bpb)], and [Cu4(μ2-I)4(μ-bpmb)4], (bpb = 1,4-bis-
significant sorption capacity towards n-octane and n-hexane. (pyrazolyl)butane; bpmb = 1,4-bis(pyrazolyl)methyl]-
Similarly, sorption with lower capacity has been observed with benzene).854 Although these compounds are nonporous in
polar molecules such as MeOH and EtOH, with the storage nature, these materials showed significant capture of volatile
capacity order, methanol < ethanol < n-hexane < n-octane. The iodine, which has been established with gravimetric uptake in
permanent porosity of these frameworks due to the presence of the range 26.0−57.9 wt %. Besides, permanent porosity in 2D
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properties and separation ability of common gases have been

explored using a variety of nanosheets and members made
from 2D MOFs.862−867 A mesh adjustable layered MOF
[Ni8(5-bbdc)6(μ-OH)4] (5-bbdc = 5-tert-butyl-1,3-benzenedi-
carboxylate)868 has been exfoliated into nanosheets of 12−40
nm thickness by mild free-thaw approach and fabricated to 2D
membranes which exhibit reversed thermo-switchable H2
permeation properties.869 A 100 nm thickness nanosheets of
2D MOF, [Zn(TCPP)] (TCPP = 5,10,15,20-tetrakis(4-
carboxyphenyl)porphyrin), form a highly permeable gutter
layer for a thin-film composite membrane.870
Kitagawa et al. utilized Langmuir−Blodgett method coupled
with layer-by-layer growth technique to integrate CoTCPP-py-
Cu 2D MOF array into Si(100) or quartz substrate surface and
to produce a MOF nanofilm (NAFS-1) composite with gate
opening features.871 Similarly, thin film of 2D MOF [Fe-
Figure 174. Honeycomb 2D layered structure of [Fe2M(O)- (py)2[Pt(CN)4] has been fabricated through liquid phase
(piv)6(bpy)1.5]·2DMF. Adapted with permission from ref 853. layer-by-layer procedure, which exhibited guest uptake via
Copyright 2011 John Wiley & Sons. structural transformation of gate-opening type, whereas the
bulk, even at a 16 nm thickness, does not show this guest
MOFs have also been exploited for the selectivity of different uptake. The effect of downsizing of the MOFs on the ethanol
gas separations.855,856 guest uptake properties has been attributed to the anisotropic
5.1.4. MOF Nanosheets. Metal-organic frameworks nano- expansion between the layers.872 Maji and co-workers
sheets have micrometer-sized lateral dimensions with thickness demonstrated a facile method to construct nanocomposites
of a few nanometers arising from several layers. 2D MOF of aminoclay with a pillared-bilayer and an interdigitated 2D
nanosheets combine the properties of 2D materials and MOFs. MOFs, [Cu(pydc)(bpp)]·5H2O and [Cu(dhbc)2(bpy)]·H2O,
The 2D nanosheets have large number of exposed active sites utilized for gas sorption.873 The former one showed improved
on its surface compared to bulk MOFs, which contain active CO2/C2H2 stepwise gated sorption by the fine tuning of
sites mostly inside the bulk. This results in the enhancement of aminoclay content, while the latter one is capable of CO2/N2
the reactivity and catalytic activity which improve their and CO2/CH4 separation under ambient conditions.
performance in sensing, catalysis, conductivity, separation, Polycationic polymers have been used via cross-linking
etc.6−17 between the polycation coils and the periphery carboxylic
Nanosheet-based molecular sieve membrane made from a groups to regulate the assembling of a 2D MOF nanosheets
2D MOF [Zn2(benzimidazole)3(OH)(H2O)]857,858 with a (∼48 nm) of Zn-TCP(Fe) to produce membranes for water
honeycomb network has an exceptional ability to separate H2/ purification by nanofiltering (Figure 175).874 This has high
CO2 gases.859 These metal-benzimidazole-based 2D MOF water permeance of 4243 L m−2 h−1 bar−1 and excellent
nanosheets of 7 nm thickness have been synthesized, and their rejection rate of organic dyes as well as salt rejection at 0.01
applications are waiting to be explored.860,861 Adsorption bar. This membrane exhibit very stable water permeance, with

Figure 175. Schematic diagram illustrating the fabrication of polycation regulated 2D Zn-TCP(Fe) membrane. Reproduced with permission from
ref 874. Copyright 2017 American Chemical Society.

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recovery up to 90% through a prolonged fouling operation. A recent study by Maji et al. showed 3D to 2D [2 + 2]
Another similar 2D MOF [Zn2(benzimidazole)4] has been photoreactive structural transformation from [Cd(pzdc)-
exfoliated to 1 nm thickness as ultrathin molecular sieve (bpe)]2·3H2O to [Cd2(pzdc)2(rctt−tpcb)]·3H2O governed
membrane and shown to exhibit H2 gas permeance of >50 000 by the presence of C−H···O interactions leading to structural
GPU with a low H2/CO2 selectivity (∼1.2) for 400 h.875 contraction and expansion, respectively (Figure 176).883 The
Although 3D MOFs have been explored extensively for the
toxic, harmful, and other pollutant gas removal from air,876
they have been extensively also explored in 2D MOFs. Arsenic
contamination in ground water is an enormous problem in
certain part of the world. Recently, a hexagonal net,
[Co3(tib)2(H2O)12](SO4)3 (tib = 1,3,5-tris(1-imidazolyl)-
benzene), has been explored for this purpose. The As(V)
adsorption capacity has been found to be 129.2 mg g−1 at 298
K.877 However, this capacity is influenced by the pH and
interfered by the presence of phosphate anions. Further, the
same 2D MOF has an excellent adsorption ability towards
Congo red up to 4923.7 mg g−1 at room temperature.878 The
uptake of Cr(VI) from waste water was also investigated by the
same group using this 2D MOF. Interestingly The maximum
uptake of 121 mg g−1 was observed at pH = 4.879 Ma and co-
workers described a 2D Cd(II) MOF [Cd(TIPA)2](ClO4)2·
3DMF·H2O (TIPA = tri(4-imidazolylphenyl)amine) as a
luminescent sensor to detect Cr2O72− anion with a detection
limit of 8 ppb as well as showed sorption capacity of 116.6 mg
g−1 through ion-exchange method.856 Safe and efficient capture
of toxic chemicals such as H2S, NH3, SO2, CO, NO2, and NO
and chemical warfare agents mostly by 3D MOFs was recently
reviewed by Farha et al.880 Another recent review by Rojas and
Horcajada dealt with the removal of organic contaminants and
pollutants from water by mainly 3D MOFs appeared.881
5.1.5. Structural Transformation. Solid-state chemical
reaction and transformation of the framework is the very
important strategy for the in situ control of sorption profile and
selectivity of gases. These chemical reactions and trans-
formations cause significant modification of inner pore walls
and lead the change in selectivity and sorption profile. This has Figure 176. (a) View of hydrogen bonding interactions before
been discussed in section 4 above. dehydration and C−H···O interactions after partial dehydration of
The ability of solid-state [2 + 2] photocycloaddition reaction [Cd(pzdc)(bpe)]2·3H2O (3D MOF). (b) View of hydrogen bonding
interactions before dehydration and C−H···O interactions after
to modify the adsorption profile of the 2D MOF, [Zn(moip)- dehydration of [Cd2(pzdc)2(rctt−tpcb)]·3H2O (2D MOF). (c)
(bpe)(DMF)], has been discussed in section 4.4.2.648 CO2 adsorption profile at 273 K and (d) methanol adsorption profile
Similarly, photoactivated functionalization of 2D interdigitated of as-synthesized MOF (black circle) and photoirradiated MOF (blue
MOF, [Zn2(N3-ipa)2(bpy)2(DMF)1.5] (N3-ipa = 5-azidoisoph- circle). Adapted with permission from ref 883. Copyright 2020
thalic acid), has also been established by the same group.882 American Chemical Society.
Because of the slight elongation in the ligand and the presence
of azide substituent, this interdigitated structure showed photoirradiated 2D MOF exhibits selective CO2 uptake
decent permanent porosity with the adsorption of N2 and compared to 3D MOF due to the lesser kinetic barrier
CO2 of 51 and 64 mL g−1 at 0.8 bar, respectively. Probably experienced by the adsorbate molecule which is supported by
because of usage of lower pressure, the gate opening MeOH sorption.
phenomenon has not been observed up to 0.8 bar pressure. In contrast to the permanent porosity and gas storage
In addition to the aromatic interactions, the layers are further capacity, the closed stacked layers of 2D structures and its
stabilized by azide−π interactions which would be another dynamic behavior under different guest sorption help in the
reason for not observing the gate opening behavior at lower enhancement of the selectivity of the gases. Webley et al.
pressure. The photo reactivate nature of the N3-ipa has been successfully carried out the transformation of porous 3D
used to capture more O2, which modifies the functional group framework with molecular formula, [Zn3(bpdc)3(bpy)], to
over the linker to both −NO and −NO2 substituents up to nonporous 2D framework, [Zn(bpdc)(bpp)] through SALE
15% conversion of N3-ipa. The preparation of this photo- (Figure 177a).884 For this, 3D MOF has been soaked in
product is not possible without the above methodology, which concentrated solution of bpp solution at 130 °C. The daughter
showed the importance of this photo-transformation method- 2D MOF showed ABAB type packing and showed no sorption
ology. The reactivity and the enhanced sorption ability during with N2 and other gases even at 10 bar. However, these
the irradiation of light has been demonstrated by O2, which frameworks displayed decent sorption properties with CO2,
showed almost the photoactivated MOF with up to 29 times along with gate opening mechanisms through dynamic layers
higher than the original dried MOF at 0.2 bar. (Figure 177b,c). Thus, the nonporous daughter framework has
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Figure 177. (a) Schematic view of preparation of 3D and 2D MOFs and (b,c) their sorption plots. Adapted with permission from ref 884.
Copyright 2015 Royal Society of Chemistry.

Figure 178. (a) Schematic diagram showing the structure of K3Fe2[PcFe-O8]. (b) Magnetic hysteresis loops for K3Fe2[PcFe-O8] are shown in the
temperature range 5−350 K. Inset: The M−H curves at 300 and 350 K. Adapted with permission from ref 893. Copyright 2019 Nature Publishing
Group.

shown better gas separation ability with selectivity CO2/N2 is fes, and kgd topologies and display antiferromagnetic, weak
80 compared to the parent 3D MOF with selectivity of only 8. ferromagnetic, ferrimagnetic, and metamagnetic properties.892
5.2. Magnetism 5.2.1.1. Ferro-, Ferri-, and Meta- Magnetic Properties. Gao
et al. reviewed this area on weak ferromagnetism in framework
Magnetism is a bulk property and transmitted efficiently structures.892 Ferromagnetic 2D MOFs with Curie temper-
through strong coordination bonds between metal centers with ature (Tc) around or above room temperature would be useful
unpaired d and f electrons and the bridging ligands in for the spintronic applications. When the canting angle, γ, is
MOFs.885 Among different magnetic properties, the long-range large, because of their spontaneous magnetization, spin canting
ordering and the spin crossover (SCO) properties are very weak ferromagnetism would also be useful as molecule-based
important in 2D MOFs. The phenomena involve the ordering magnets.
of electrons through an external stimulus and are very Recently, a layered MOF, K3Fe2[PcFe-O8] ([PcFe-O8] =
important in data storage and electronics.886−891 The long- [(2,3,9,10,16,17,23,24-octahydroxy phthalocyaninato)Fe], Fig-
range ordering properties in 2D MOFs are discussed first. ure 178a), shows spontaneous magnetization and super-
5.2.1. Long-Range Ordering. The distance between the paramagnetic features at 350 K. This also exhibits semi-
spin centers is critical for the ordering temperature. The conducting nature at room temperature with carrier mobility of
bridging ligands such as azide, thiocyanate, and carboxylates 15 ± 2 cm2 V−1 s−1 measured using terahertz spectroscopy.
are often used to form different types of 2D MOFs with sql, Variation of the magnetization with the applied magnetic field
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(M−H curves) measured at different temperatures (5−350 K)

is shown in Figure 178b. The magnetic hysteresis with
saturation magnetization of ∼0.13 μB per Fe-site is shown at
350 K. These results suggest the presence of super-
paramagnetic behavior as well as ferromagnetic coupling with
Curie temperature higher than 350 K. The DFT calculations
reveal an exchange energy ∼300 meV and also negative
magnetoresistance at 300 K.893
Before this work, first-principles calculations by Dincǎ and
co-workers on similar 2D MOFs with M = Cr, Mn, Fe, Co, Ni,
Cu, and Zn predicted the ferromagnetic ordering temperature
exceeded 600 K, but the Monte Carlo calculations that
includes magnetic anisotropy predicted a Tc of 170 K for the
NiMn MOF. The design strategy realize ferromagnetism in 2D
MOFs with high Tc should include a strong hybridization
between the open-shell ions and the delocalized aromatic π
systems with appropriate symmetry and large magnetic
anisotropy.894
A few 2D MOFs have been reported to have ferromagnetic
ordering and spin canting well below room temper-
atures.895−918 On the contrary, ferromagnetic behavior
including ferromagnetic ordering, spin-canting, and spin-glass
like behavior has been observed only in a few 2D
MOFs.692,919−925 A few reports discussed the presence of
ferrimagnetism in 2D MOFs.919−924
Metamagnetism arises from a sudden increase in the
magnetization with a small change in the external applied
magnetic field. Metamagnetism is a special type of anti-
ferromagnetism in 1D or 2D systems with competing magnetic
interactions.926 The 2D MOF [Cu3(N3)6(DMF)2] form 1D
ferromagnetic chains by Cu2(μ1,1-N3)4, which run parallel to
the a-axis. These chains are linked by the μ1,3-N3 bridging to
form the layer in the ab plane (Figure 179a) and responsible
for the weak antiferromagnetic coupling, which leads to
antiferromagnetic ordering below 5 K (Figure 179b). This
coupling is weak enough by the moderate field 2.7 T at 2 K to
provide a metamagnetic spin-flop transition with a small
hysteresis (0.2 T).927 Two more MOFs with azide ligands also Figure 179. (a) View of the sheet structure. (b) Magnetization
show metamagnetism below 10 K.924 In some cases, the isotherms of [Cu3(N3)6(DMF)2]at different temperatures with
metamagnetic behavior is also modulated by solvent928 and increasing fields. The lines are Brillouin curves for S = 3/2 and g =
further accompanied by magnetic relaxation733,929,930 and spin 2.1 at these temperatures. The inset shows the derivatives dM/dH at
canting.931−933 various temperatures, revealing the 2 K spin-flop field at 2.7 T.
5.2.1.2. Antiferromagnetic Properties. Lack of inversion Adapted with permission from ref 927. Copyright 2009 Royal Society
center in local symmetry between the two coupling spin of Chemistry.
carriers is responsible for the spin canting that arises from the
antisymmetric exchange. Antiferromagnets frequently exhibit and the evacuated sample behaves as a paramagnet in this
such spin canting, where the spin carriers are linked by temperature range.
monoatomic bridges.926 Further, the most frequently encoun- A rectangular 2D MOF, [Cu(HF2)2(pz)], is reported to be
tered magnetic properties in 2D MOFs is the antiferromag- made up of Cu(pz) chains connected by doubly bridging via
netic ordering, and this is dominated in the Cu(II) containing μ1,3 and μ1,1 linkage of HF2− anion to furnish a 2D sheet
2D MOFs. 896−899,919,934−949 Several Mn(II) and Co- structure (Figure 180a). Here, the HF2− anion is assumed to
(II),196,900−902,929−932,950−966 and a few Fe(II) and Ni(II) be a covalently inorganic bonded ligand due to strongest H···F
2D MOFs with mostly containing (4,4) grid structures have bond. This exhibits an antiferromagnetic behavior with a
also exhibit this antiferromagnetic ordering.734,903−905,967−970 weaker spin exchange through the pz bridge (Figure 180b).972
An organic free radical functionalized carboxylate, PTMTC Five layered MOFs, [Fe(bimX)2] (HbimX = benzimidazole
containing hexagonal 2D MOF, [Cu 3 (PTMTC) 2 - with the 5-position X = H, Cl, Br, Me, or NH2), can be
(py)6(EtOH)2(H2O)] (PTMTC = tris(4-carboxy-2,3,5,6-tetra- mechanically exfoliated. These materials increase their
chlorophenyl) methyl radical), with very large pores (2.8−3.1 processability and stability and can be functionalized post-
nm) has been successfully made as a magnetic solvent sensor. synthetically and anchored on surfaces. They retain long-range
This MOF exhibits a reversible and highly selective solvent- structural order and exhibit antiferromagnetic properties.973
induced breathing process which has strong influence on the 5.2.1.3. Magnetic Properties of Kagomé 2D MOFs. Spin
magnetic properties of this materials.971 The as-synthesized systems on Kagomé type 2D MOFs with (6,3) topology
MOF shows long-range antiferromagnetic ordering below 2 K, (section 2.3.5) are the abundant system to study the quantum
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In 2002, Zaworotko et al. reported the first Kagomé lattice in

a 2D MOF, [(Cu2(py)2(1,3-bdc)2)3], in which the 4-
connected paddlewheel are linked by the 1,3-bdc ligand as
shown in Figure 182a. In this geometrically frustrated
antiferromagnetic state with d9 Cu(II) atoms, the field-
dependent magnetization data shows a well-defined hysteresis
loop indicative of the ferromagnetic behavior at 5 K (Figure
182b). The triangular Kagome lattice results in the disruption
of perfect antiferromagnetic ordering (Figure 182c) by
introducing spin frustration that leads to canted arrangement
of spins and the appearance of effective weak ferromagnetic
long-range order.368
Chen et al. investigated [Co3(μ3-OH)2(1,2-chdc)2] (chdc =
trans-1,2-cyclohexane dicarboxylate) comprising triangular
arrays (Figure 183) to exhibit the coexistence of spin
frustration and long-range magnetic ordering. The χT vs T
curve characteristic of antiferromagnetism in [Co3(μ3-
OH)].975 In a similar pseudo-Kagomé lattice, [Co3(μ3-
OH)2(BTP)2] (BTP = 4-(3-bromothienyl)phosphonate))
composed of corner-sharing irregular triangles of [Co3(μ3-
OH)], was reported to have a long-range ferromagnetic
ordering below 30.5 K with a coercivity (Hc) of 5.04 kOe at 5
K. By reducing the particle size to the nanoscale region, the
soft magnet becomes one of the hardest molecule-based
magnets.920 The magnetic properties of a few Kagomé lattices
have been reported.976−981
A citrate bridged Dy(III) 2D MOF, [Dy(citrate)(H2O)], is
reported to have an unusual magnetic relaxation behavior due
to geometrical frustration resulting from the alternative
arrangement of square and triangle grids.982
Two heterobimetallic 2D MOFs, [Cu2M(tzdc)2(H2O)2]·
2H2O, (M = Fe(II), Mn(II) and tzdc = 1,2,3-triazole-4,5-
dicarboxylate), generate mixed-spin Kagomé layers arising
from different metal ions (Figure 184).692 The variable
Figure 180. (a) View of 2D MOF [Cu(HF2)2(pz)]. (b) Magnetic temperature magnetic studies (χT vs T) in the range 300−
susceptibility plot highlighting the low-T peak and isothermal 100 K show the dominance of the antiferromagnetic coupling.
magnetization (inset) for [Cu(HF2)2(pz)]. Adapted with permission Therefore, the ferrimagnetic behavior is due to incomplete
from ref 972. Copyright 2011 John Wiley & Sons. cancellation of antiferromagnetic coupling between Cu(II) and
Fe(II)/Mn(II) through anti−anti carboxylate bridges within
the mixed-spin Kagomé layers. No long-range magnetic
electronic states due to its high degree of frustration (Figure ordering was observed in both above 1.8 K.692
181). Such a geometric frustration gives rise to “order by 5.2.1.4. Magnetic Properties of Rare Earth Metal Ions.
disorder” or quantum spin liquid, and hence this system is a Magnetic properties of the lanthanide(III) containing materi-
good platform to design spintronic materials.974 als, arising from the unfilled 4f orbitals, are due to different
space orientations. This provides magnetic anisotropy that
influences the coercive field.983 Among lanthanide(III) ions,
Dy(III) ion contains unique 4f orbital electrons and exhibit
strong spin-orbit coupling and high magnetic moments. Hence
this has been used as a metal node of choice to construct to
design lanthanide-based MOFs. Several of these 2D MOFs
have single-molecule magnet (SMM) behavior, which feature
slow magnetic relaxation at low temperatures and magnetic
hysteresis.984,985 The single reversal energy barrier μeff and the
magnetic anisotropy of the spin carriers are among the
important ones to be considered for the SMM. They are
potential candidates for high-density information storage,
quantum computing, and spintronics.
Gao et al. reported a layered MOF [Dy(L)(ox)0.5(OH)-
Figure 181. Kagomé lattice with spins in one possible ground-state
configuration. Note that the spins on a hexagon can be rotated out of (H2O)] (L = 2-(3-pyridyl)pyrimidine-4-carboxylate) in which
the plane about the dotted ellipse without changing the energy, thus the connectivity of L with Dy(III) generated 1D chains with
giving rise to an infinite number of degenerate ground states. Dy···Dy distance of 3.878 Å. The adjacent 1D chains are
Reproduced with permission from ref 974. Copyright 2004 John connected by oxalate to produce the layer structure with Dy···
Wiley & Sons. Dy distance of 6.283 Å. Magnetic studies of this MOF
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Figure 182. (a) View of the Kagomé lattice of [(Cu2(py)2(1,3-bdc)2)3]. (b) Temperature dependent molar susceptibility at 0.1 T, J = −350 cm−1.
(c) The field-dependent magnetization at 5 K. (b,c) Adapted with permission from ref 368. Copyright 2002 John Wiley & Sons.

behavior below 50 K,1000 and spin glass like unusual field

dependent magnetic relaxation.1001
Multiferroic properties have been rarely observed in 2D
MOFs. An interesting [TbL2(H2O)2](ClO4) (L = lactate)
crystallized in the space group C2 shows both ferromagnetic
and ferroelectricity. The connectivity of lactate with Tb(III)
provides a layered structure. The temperature dependence
magnetic susceptibility measurements in Figure 185a shows
ferromagnetic coupling between the Tb(III). Further, the
Figure 183. (a) View of the environment around the Co(II) atoms.
(b) 2D Kagomé lattice. Adapted with permission from ref 975.
ferroelectric behavior of this MOF was confirmed from the
Copyright 2006 Royal Society of Chemistry. electric hysteresis loop with remnant polarization of about 0.25
μC cm−2 and coercive field of 0.2 kV cm−1 (Figure 185b).
However, the saturation spontaneous polarization is ∼0.1 μC
cm−2 was smaller than the KDP. The dielectric permittivity of
the powdered samples was also measured at different
frequencies and temperatures for this probably the first
multiferroic 2D MOF.1002
Another interesting strategy to design the multiferroic
material is to combine a ferroelectric 4-aminopyridinium
Figure 184. Schematic diagram showing the bonding modes of the cation with a magnetically dominant bimetallic oxalate anion,
ligand tzdc responsible for the mixed-spin Kagomé in [Cu2M- [Mn(II)Cr(III)(ox)3(C2H5OH)]− (Figure 186). The resultant
(tzdc)2(H2O)2]·2H2O. Reproduced with permission from ref 692. 2D MOF crystallized in the noncentrosymmetric space group
Copyright 2010 American Chemical Society. Pna21 shows second harmonic generation, ferromagnetic
ordering, and ferroelectricity.1003
5.2.2. Valence Tautomeric Transitions Containing
highlight the presence of ferromagnetic interactions between Co(III) 2D MOFs. Valence tautomeric (VT) transitions are
the Dy(III) atoms, slow magnetic relaxation with an effective most commonly observed for Co(III)-dioxolene systems. This
energy barrier μeff of 186 K under zero dc field with involves intramolecular electron transfer and concomitant spin
pronounced hysteresis loops at low temperature. The factor transition at the cobalt center, from low-spin Co(III)-
α parameter, 0.071−0.14 at 20−30 K indicates a single catecholate at low temperature to high-spin-Co(II)-semi-
relaxation process.986 According to the authors, the energy quinonate upon heating.1004 The SCO and VT transitions
barrier is the largest among such 2D MOFs. involving Co(III) are prevalent in 1D CPs.
SMM987 and slow magnetic relaxations988−994 are the An interesting 2D MOF containing 3,5-di-tert-butylcatecho-
common feature in Dy(III) MOFs. Interestingly, a Gd(III) late (BCat) and its semiquinone form (Bsq), [{Co(BCat)-
MOF is reported to exhibit magnetocaloric effect,995 whereas (Bsq)} 2 (TPOM)]·2EtOH·8H 2 O (TPOM = tetrakis(4-
Er(III) and Gd(III) 2D MOFs display antiferromagnetic pyridyloxymethylene)methane), has a highly corrugated (4,4)
interactions.993,996,997 A number of heterobimetallic MOFs net. This undergoes thermal- and photoinduced valence
containing Cu(II) and lanthanide(III) have been investigated tautomeric transitions (Figure 187).1004,1005 When the sample
for magnetic properties such as SMM,998,999 ferromagnetic is cooled from 350 to 5 K, the χMT value decreases gradually to
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Figure 185. (a) Temperature dependence of magnetic susceptibilities are plotted for χmT and χm at an applied field of 2 kOe from 1.8 to 300 K. (b)
Electric hysteresis loop of a pellet of powders observed by an RT6000 ferroelectric tester at room temperature. Adapted with permission from ref
1002. Copyright 2008 American Chemical Society.

In 1985, Reedijk et al. reported probably the first SCO in a

2D MOF. The Fe(II) MOF [Fe(NCS)2(btr)2] (btr = 4,4′-bis-
1,2,4-triazole) undergoes a 40% HS to LS transition at 153
K.1010−1012 The temperature dependence of the χMT and 57Fe
Mössbauer spectral measurements of 2D MOF with fes
topology shows the existence of HS ↔ LS SCO transition in
equilibrium below room temperature. 1013 Two highly
corrugated 2D MOF with (4,4) grid structures exhibit SCO
behavior with spin transition temperatures of 416 and 419
Figure 186. (a−c) Design strategy for making multiferroic 2D MOF K.1014 A 2D to 3D polycatenated MOF, [Fe2(pptp)4·2H2O]
material by combining ferromagnetic anions and ferroelectric cations. (Hpptp = 2-(3-(4-(pyridin-4-yl)phenyl)-1H-1,2,4-triazol-5-yl)-
Reproduced with permission from ref 1003. Copyright 2012 John pyridine), showing guest-dependent SCO transition temper-
Wiley & Sons.
ature at 390 K with 20% high-spin character has also been
reported.1015 SCO behavior induced by thermal changes,
the value 0.4 cm3 K mol−1, typical of an Sq radical (S = 1/2) pressure, or light has been observed in a number of 2D MOFs
between 220 to 5 K. Upon heating, when the χMT value with (4,4) topology containing Fe(II).1016−1023 Further, such
reached 0.89 cm3 K mol−1 at 314 K, electron transfer from the HS ↔ LS transitions have also been encountered in 2D MOFs
Cat2− ligand to the CoIII center, resulting in a population of with topologies like hxl1024 and kgd.1025 Many of these
CoII−Sq*−−Sq*− isomer. transitions are accompanied by visible color changes of the
5.2.3. Spin Crossover (SCO). The SCO materials are able solids.
to switch from low spin (LS) to high spin (HS) states when Real et al. observed SCO to take place in two steps in
heated. This conversion occurs when the entropy term TΔS [Fe(bpy)2(NCX)2]·4CHCl3 (X = S and Se). The S-derivative
compensates the enthalpy differences, ΔH. This phenomenon has critical temperatures T1/21↑,↓ = 143.1, 150.7 K, and T1/22↑
is found in the first-row transition metal complexes with d4−d7 ,↓ = 91.2, 112.2 K, whereas Se-derivative displays half-spin
configuration. Of these, the largest number of examples are transition characterized by T1/2↑,↓ = 161.7, 168.3 K. Both 2D
found in the octahedral Fe(II).102−104,1004,1006−1009 Apart from MOFs display a change in the space groups from P2/c to C2/
heat, pressure or light may also induce such spin transitions. c.1026
For example, the SCO accomplished by the irradiation of light Tong et al. reported two-step SCO properties at high
is called “light-induced excited spin state trapping” (LIESST). temperatures in two 2D MOFs, [Fe(bpt)2] and [Fe(Mebpt)2]

Figure 187. (a) Two views of the (4,4) layer structure generated by the tetrahedral TPOM ligand and angular Co(III) center. (b) χMT vs T plots
for heating and cooling cycles. Adapted with permission from ref 1005. Copyright 2011 American Chemical Society.

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Figure 188. (a) Coordination environments of Fe1 and Fe2. (b) 2D (4,4) rhombic grids in [Fe(Mebpt)2]. (c) DSC curves of [Fe(bpt)2] (in
green) and [Fe(Mebpt)2] (in purple). (d) Experimental (dotted) and simulated (solid) χMT vs T curves of these two 2D MOFs in the temperature
range of 200−600 K. (e) Relative intensity of the doublet (1580/1600 cm−1) vs T obtained from variable temperature Raman spectra of
[Fe(Mebpt)2]. Adapted with permission from ref 1027. Copyright 2012 Royal Society of Chemistry.

(bptH = 3-(2-pyridyl)-5-(3-pyridyl)-1,2,4-triazole and 2,3- as shown in Figure 189.886,895,1032 On irradiation with a 647
MebptH = 3-(3-methyl-2-pyridyl)-5-(3-pyridyl)-1,2,4-tria- nm wavelength laser, the LIESST was observed.895,1033,1034
zole), shown in Figure 188a,b. The critical temperatures Pressure and light-induced bistability has been observed in
T1/2↑,↓ = 329, 501 K, and 351, 520 K respectively, are the
other 2D motifs also.1028,1035
highest critical temperatures reported confirmed by X-ray
crystallography, magnetic susceptibility measurements, DSC,
Raman, and Mössbauer spectroscopy.1027 Figure 188c−e
shows DSC, Raman, and VT magnetic susceptibility measure-
ment studies.
Guest modulated two-step SCO behavior with different
transition temperatures, hysteresis widths have been encoun-
tered by Chen et al.1028 In the case of [Fe(4-bphz)2(NCS)2]
(4-bphz = 1,2-bis(pyridine-4-ylmethylene)hydrazine), the
SCO behavior disappears when the guest molecules changed
from MeCN to nitrobenzene or naphthalene.1029 A few more
two-step SCO in Fe(II) 2D MOFs have been reported in the
literature.1021,1030,1031
Coexistence of both magnetic ordering and photoinduced
SCO (LIESST effect) was realized in the hexagonal 2D MOF
[FeIII(sal2-trien)][MnIICrIII(ox)3]·DCM (H2sal2-trien = N,N′-
disalicylidenetriethylene-tetramine). Above 350 K, this MOF is
Figure 189. Magnetic and photomagnetic behavior of [FeIII(sal2-
in the HS state over 80%. The HS ↔ LS takes place in the trien)][MnIICrIII(ox)3]·DCM. Magnetic behavior measured in dark
temperature range 350−165 K, and the χMT reaches gradually (filled square) and the photomagnetic behavior measured after
to 94% LS below 165 K. Below 165 K, χMT increases due to irradiation by 647 nm wavelength laser (open square). Inset: Curie−
the MnII−CrIII ferromagnetic interactions within the bimetallic Weiss law between 50 and 150 K. Reproduced with permission from
oxalate layers with long-range ferromagnetic ordering at 5.6 K ref 895. Copyright 2011 Royal Society of Chemistry.

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An interesting bimetallic 2D MOF [Fe(bpy)2Hg(SCN)2] as methylpyridine derivative exhibits a two-step transition with
shown in Figure 190a exhibits HS ↔ LS spin transition hysteresis. The formation of a mixture of HS and LS states
occurs at 70 K when cooled from room temperature. The pure
HS state is restored when heated above 120 K. The second
SCO transition to the pure LS state occurs below 70 K. By
applying external pressure (0.18−0.58 GPa), increase in
pressure to 0.86 GPa converts this into a one-step
transition.1049 Similar Hofmann-type 2D MOFs containing 3-
chloropyridine and 3-fluoropyridine also exhibit two-step SCO
but not 3-iodo and 3-bromo derivatives in [Fe(3-
Xpyridine)2[Ag(CN)2] (X = F, Cl, Br, and I).1050 When
Ag(I) was replaced by Au(I), the SCO behavior was
different.1051 A two-step SCO transition was observed in
[Fe(3-Ipy)2[Au(CN)2]·1/2(3-Ipy) (where 3-Ipy = 3-iodopyr-
idine) with critical temperatures of T1/21 = 155 K, T1/22↑ = 97
K, and T1/22↑ = 110 K. Because of the strong Au···Au
interactions, double layers are formed. The N···I supra-
molecular interactions between the N atoms in the guest 3-
Ipy and I of the coordinated 3-Ipy injected extra electron
density to the Fe(II) site and thus responsible for the two-step
SCO process.1051 Kitazawa et al. have also reported such a
guest dependent SCO transition.1052 In the Hofmann-type
structure, [FeX2(Au(CN)2)2]·X (X = 4-(3-phenyl)pyridine),
the guest containing MOF shows a two-step SCO at T1/2↑,↓ =
92.5, 93.4 K and second one at T1/2 = 250 K with no
hysteresis. On the other hand, the 2D MOF without the guest
shows a single-step SCO at T1/2 = 124 K.1052
A two-step SCO behavior was observed in the case of
Figure 190. (a) View of the 2D MOF. (b) Temperature dependence [Fe(thtrz)2Pd(CN)4]·EtOH·H2O (thtrz = N-thiophenylidene-
of χMT, scaled to γHS, measured at a 1 K min−1 cooling rate. (c) Unit 4H-1,2,4-triazol-4-amine). Interestingly, it shows a record-
cell volume given in the (a,b,c) cell of the HS and LS phases. Adapted breaking 120 K intermediate plateau region between the two
with permission from ref 1036. Copyright 2016 John Wiley & Sons. steps stabilized by negative cooperative interactions (Figure
191).1053 Two-step SCO transition with different types of
involving staircase-like multistep SCO (Figure 190b). Two hysteresis has been observed in several similar Hofmann-type
steps associated with different ordering between the fully HS 2D MOFs also.655,1047,1052,1054−1061
(γHS = 1) and LS (γHS = 0) appear in terms of spin-state The effect of pressure on the SCO properties have also been
concentration waves (SSCW). Crystallographic structures investigated along with the influence of
reveal an aperiodic SSCW with a HS−LS sequence
incommensurate with the molecular lattice.1036
5.2.3.1. SCO in Hofmann-Type 2D Structures. The
Hofmann-type of 2D MOFs has been discussed briefly in the
section 2.3.2.1. Tong et al. in 2017 reviewed the SCO behavior
in these types of structures.103 The 2D MOF [Ni(NH3)2[Ni-
(CN)4]·2C6H6 with diamagnetic square-planar [Ni(CN)4]2−
ions and paramagnetic octahedral [Ni(NH3)2(CN)4]2+ ions, is
an antiferromagnet with a typical Ising spin system and
transition point at TN = 2.39 K and displays antiferromagnetic
ordering.1037 The SCO in Hofmann-like Fe(II) compound was
observed in [Fe(py)2[Ni(CN)4]·2C6H6 with T1/2↑,↓ = 170,
210 K due to S = 0 to S = 2.1038 Since then, there has been
ongoing discovery of new 2D MOFs with similar behav-
ior.1039,1040 These are a promising class of switchable
molecular materials for memory devices. Magnetic hysteresis
can be tuned by taking advantage of the intermolecular
interactions in order to generate close contacts amongst
molecules and allow spin change to propagate efficiently
throughout the lattice. A number of Hofmann-type 2D MOFs
Figure 191. Representation of (a) a single [FePd(CN)4] grid and (b)
containing Fe(II) have been found to show single-step SCO two layers of the grid highlighting the arrangement of HS and LS
behavior.1019,1020,1041−1048 iron(II) sites at IP temperatures. (c) χMT versus temperature (1 K
The 2D MOFs [Fe(L)2[Ni(CN)4] (L = 2- and 4- min−1). Cooling (blue) and heating (red) curves. Inset: schematic of
methylpyridine) remain in the high-spin (HS) state at room HS (yellow)−HS to HS−LS (purple) to LS−LS transition of Fe1 and
temperature and at atmospheric pressure. They undergo SCO Fe2 (interactions). Adapted with permission from ref 1053. Copyright
to low spin (LS) state when cooled to below 5 K. However, 3- 2014 Royal Society of Chemistry.

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heat.1007,1020,1049,1051,1057,1062−1064 The Hofmann-type 2D space groups that are either chiral or unsymmetrical in nature,
MOF [Fe(4-phpy)2Ni(CN)4]·H2O (4-phpy = 4-phenylpyr- through the homochiral systems and helical struc-
idine) undergoes SCO at T1/2↑,↓ = 134, 143 K. When a green tures.1078−1084
laser (λ = 532 nm, 150 mW) was illuminated this MOF at 5 K, Janiak and co-workers reported the second-order nonlinear
an increase in the dc susceptibility suggested LS ↔ HS effects in a 2D MOF, [(HB(C2H2N3)3)Ag] (HB(C2H2N3) =
transition, exhibiting the LIESST effect.1065 Several 2D MOFs hydrotris(1,2,4-triazolyl)), in 1996.1085 In this structure which
of Hofmann-type have been found to exhibit this prop- belongs to the acentric space group Pna21, both Ag(I) and B
erty.1056,1057,1066−1068 atoms are present in tetrahedral coordination geometry.
The SCO property of the 2D MOF materials in nanoform Interestingly, this compound does not show any absorption
have been found to depend on the environment within the in the range 300−3000 nm but shows a significant SHG
nanocomposites as well as the shape and size of the behavior with the nonlinear coefficient that is very similar to
nanocrystals.104,1069,1070 The density function theory (DFT) quartz.
has been used to investigate the SCO in these systems.1071 Lin’s group has contributed significantly to the development
Recently, both epitaxial thin-films and single crystals of a series of the second-order NLO effects in MOFs. This group
of 2D Hofmann-type compounds, [Fe(L)2M(CN)4]·xH2O (L presented the synthesis of two 2D layered MOFs, [Zn(nic)2]
= py, pyrimidine, isoquinoline; M = Ni, Pd, Pt) have been (nic = nicotinate) and [Cd(L1)2] (L1 = 3-[2-(4-pyridyl)-
examined for cooperative SCO properties.1072 As an example, ethenyl]benzoate) (Figure 193), in which the asymmetrical
in case of [Fe(pyrimidine)2Ni(CN)4]·xH2O, thermal depend-
ence of χMT with HS FeII state was observed at 105 GPa and
low temperature attributed to zero-field splitting of the S = 2
state. However, nearly complete cooperative SCO accom-
panied by a thermal hysteresis appeared at 0.34 GPa with little
change in HS↔LS. On the other hand, complete SCO
property is observed at 0.5 and 0.74 GPa characterized by
[T1/2↓ = 176 K, T1/2↑ = 198 K, and ΔT1/2 = 22 K (T1/2av = 187
K)] and [T1/2↓ = 213.5 K, T1/2↑ = 237.0 K, and ΔT1/2 = 23.5 K
(T1/2av = 225 K)] (Figure 192).

Figure 193. 2D grid structures of (a) [Zn(nic)2] and (b) [Cd(L1)2].

Adapted with permission from ref 1077. Copyright 2012 American
Chemical Society.

linkers coordinate in bent mode to avoid the center of

symmetry in the material.1086 These 2D MOFs are chiral in
nature, with acentric 2D square grids through the meta-
substituted pyridyl-carboxyl groups. The Zn(II) MOF crystal-
lized in P43212, chiral space group, whereas the Cd(II) MOF
crystallized in acentric space group, Fdd2. Both materials
showed SHG behavior. Because of the long linker, the Cd(II)
MOF is 3-fold interwoven with rhombohedral grids with
Figure 192. χMT vs T plots for [Fe(pyrimidine)2Ni(CN)4]·xH2O. opposite chirality and formed 2D racemate. The SHG
Adapted with permission from ref 1072. Copyright 2020 American efficiency (I2ω) of the Zn(II) MOF is 2 Vs α-quartz, confirmed
Chemical Society.
through Kurtz powder measurements, whereas the SHG
efficiency of the Cd(II) MOF is 1000 Vs α-quartz or larger
5.3. Second-Order Nonlinear Optical (NLO) Properties than LiNbO3.
The second-order NLO properties or the second harmonic Later, broader studies with significantly higher collection of
generation (SHG) effects observed in materials that are frameworks through the usage of more ligand with meta- or
crystallized either in chiral or noncentrosymmetric space bent-coordination have been reported by the same group.1087
groups. These NLO materials are not only useful for the Meanwhile, usage of Zn(II) or Cd(II) metals (d10) that are
frequency doubling in the laser industry but also the key to the coordinated either tetrahedral manner or cis-octahedral
future photonic technologies.1073−1075 The challenges involved coordination also assisted in the preparation of acentric
in the rational design of these MOFs with the desired metal coordination sphere, to impart the acentric character in the
nodes and linkers as NLO materials was reviewed by Lin et packing of these materials. Hence this strategy was successfully
al.1076,1077 These materials can be designed either by the usage established to rationally design SHG materials. Because of the
of chiral and achiral linkers or using donor−acceptor and presence of pyridyl group as well as carboxylate, there is also
push−pull strategies. electronic asymmetry (donor−acceptor) in the framework
5.3.1. Chiral and Achiral Linkers. The coordination of which further broadened the scope for the better NLO
achiral linkers can be successfully crystallized in either chiral or characteristics and efficiency. The SHG efficiencies (I2ω) of
noncentrosymmetric space groups in the resultant 2D MOFs. these materials are ranged from 2 to 800 Vs α-quartz. Similar
This could be due to the presence of steric hindrance in the concepts of bent coordination has been used for the
coordination sites which helps to crystallize the materials in preparation of 2D MOF for NLO studies.1088
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The same group later reported an octupolar coordination

network, [Cd3(μ3-OH)(L)3(py)6](ClO4)2, using trimetallic
node with triangular node, M3(μ3-OH) with organic linker,
4-[2-(4-pyridyl)ethenyl]benzoate (L).96 This compound crys-
tallized in chiral space group R32 with 2D network as shown in
Figure 194. The SHG efficiency of this compound has 10 times
higher efficiency than the KDP.

Figure 195. (a) View showing single wavelike sql grid and (b) double
helical structure of the linkers. Reproduced with permission from ref
1093. Copyright 2010 American Chemical Society.

2.8 and 2.6 times that of KDP respectively for Zn(II) and
Cd(II) MOFs.
Usage of similar strategies with the chiral linker has been
used in the preparation of MOFs, which are either crystallized
in chiral space groups or noncentrosymmetric space groups,
Figure 194. (a) View of the [Cd3(μ3-OH)(L)3(py)6] building block. which were explored for the second-order NLO character-
(b) View of the 2D MOF with hxl topology. Adapted with permission
from ref 96. Copyright 1999 American Chemical Society.
istics.329,1094−1098
5.3.2. Donor−Acceptor or Push−Pull Mechanism.
Donor−acceptor and push−pull are the other important
strategies to design the materials with NLO properties.
Along with transition metals, lanthanide 2D MOFs have also Xiong et al. presented couple of interesting examples with
been established to observe the NLO properties. During this these concepts where donor−acceptor is with 2D square grid
process, [Eu(cda)3(H2O)3]·H2O (cda = carbamyldicyanome- networks, [Zn(CN4-C6H4-C12H7NC5H4N)2]·1.5H2O1099 and
thanide anion) has been crystallized in the space group, Cc.1089 [Mn(H-DNTY)2]1100 (H2-DNTY = 3,5-dinitrotyrosine).
The Eu(III) is present in unidentate ligand via nitrile-nitrogen These compounds crystallized in noncentrosymmetric space
atom to form 2D layered structure. The SHG efficiency of the groups with strong charge transfer in the framework along with
compound is ∼16.8 times that of urea. strong hyperpolarizability in the framework through the
Chen’s group has used achiral bridging ligands such as hip specific packing of the molecules. In addition, the presence
and 2,2′-bpy (hip = 4-hydroxyl-isophthalate) to synthesize two of a chiral amino acid as the part of the linker in Mn(II) MOF
2D isostructural MOFs, [M3(2,2′-bpy)3(hip)2]·5H2O (M = further assisted in the enhancement in the NLO activity along
Zn, Co). The connectivity of ligands around the trimetallic with the H-bonds in the framework, resulted in the efficiency
cluster building blocks generated the sql net.1090 These layers up to 50 and 6 times that of urea, respectively. Similar strategy
are stacked in ABAB manner, and this compound crystallized further used by other groups to obtain similar NLO
in the space group P21. This chiral packing of the framework characteristics.323,1101,1102
has been established through SHG measurements with Anthony and Radhakrishnan employed the push−pull
efficiency of the compounds 0.5 and 0.02 relative to that of mechanism along with chiral ligand to impart the second-
urea, respectively. The same group reported two chiral 2D order NLO effect in 2D framework, [Cu(BCDC)]PF6·THF
MOFs through in situ generation of ligands, namely, [Zn(2- (BCDC = N,N′-bis(4-cyanophenyl)-(1R,2R)-diaminocyclo-
pc)(4-pc)] and [Cd(2-pc)(4-pc)(H2O)]·N2H4 (2-pc = 2- hexane).1103,1104 Because of the presence of a chiral linker as
pyridinecarboxylate; 4-pc = 4-pyridinecarboxylate), crystallized shown in Figure 196, the compound crystallized in chiral space
in the space groups Pna21 and P21, respectively.1091,1092 The
efficiency of these MOFs has been estimated as 3.5 and 1.5
times that of KDP respectively.
Similar in situ preparation of organic ligands has been
established for the preparation of uranyl 2D MOFs.136
[UO2(opyca)2] (opyca = 1-oxo-4-pyridylcarboxylate) and
homochiral [UO2(L)] (L = uranyl-bis[(S)-lactate] have been
obtained through the reaction of UO2(NO3)2 with 1-oxo-4- Figure 196. (a) Chemical structure of BCDC along with the package
cyanopyridine (ocpy) and ethyl (s)-lactate(e-la). These chiral of BCDC linker in (b) [Cu(BCDC)]PF6·THF. Adapted with
2D MOFs showed NLO activity (0.4 and 0.1 times that of permission from ref 1103. Copyright 2004 Royal Society of
urea) as they are crystallized in chiral space groups, P212121 Chemistry.
and P21, respectively.
The Qian’s group has employed the strategy of using chiral
linkers for making noncentrosymmetric MOFs. This is
illustrated in two chiral 2D MOFs, [M(L)2(H2O)2] (M = group, P212121 and the orientation of BCDC (both exo
Zn and Cd; L = 1,2,2-trimethyl-3-(pyridin-4-ylcarbamoyl)- conformation and the torsion angle at the amino sites)
cyclopentanecarboxylic acid), which exhibit interwoven (4,4) facilitated further enhancement of chirality followed by the
square grids of double helices as shown in Figure 195.1093 The potential second-order NLO activity in the framework. The
2D layers of MOFs are stacked in ABAB packing manner in the Cu(I) MOF gave a moderate activity of 0.3 times that of urea,
chiral C2 space group. The presence of chiral and helical linker while the Ag(I) MOF causes a nearly ten-fold increase in the
contributed to the second-order NLO effects with efficiencies SHG to 2.9 times that of urea. This polarization in the linker
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Figure 197. (a) Coordination mode and the core structure of H3TTAA ligand. (b) Crystal structure of chiral 2D MOF (H2NMe2)[Cd(TTAA)]·
2H2O. Relative emission spectra of (c) (H2NMe2)[Cd(TTAA)]·2H2O and (d) (H2NMe2)[Cd(TTAA)]·H2O with the variation of their
fluorescent quantum yields (λexc = 318 nm) in the solid state at 77 and 298 K. Inset: fluorescent image of the bright-blue luminescing frameworks at
298 K. Adapted with permission from ref 1108. Copyright 2012 Royal Society of Chemistry.

also has been established through the semi-empirical computa- = 300 nm) is found in a 2D to 3D polythreaded MOF
tional studies. [Pb(Hmpda)(bibp)Cl]·H2O (H2mpda = m-phenylenediacetic
Some of these 2D MOFs show both NLO and ferroelectric acid; bibp = 4,4′-bis(imidazol-1-ylmethyl)biphenyl).1110 Some
properties.136,1080,1093 In addition to the second-order non- other 2D MOFs with blue or blue-green emissive nature are
linear effects such as SHG, there are several higher-order NLO found in the literature.1111−1115
effects such as third harmonic generation and multiphoton 4,4-Difluoro-4-bora-3a,4a-diaza-sindacene (BODIPY) is a
absorption that have been recently established in MOFs.1074 well-known fluorophore moiety that has been used as a tag to
However, no significant studies have been established towards construct 2D MOFs such as [Cd2(L)(bpee)3(NO3)2]·2H2O·
2D MOFs. DMF·EtOH and [Cd(L)(bpee)0.5(DMF)(H2O)] (H2L = 2,6-
5.4. Luminescence dicarboxyl-1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradia-
zaindacene), with orange-red emissiona at 574 and 596 nm,
A broad range of MOFs have intrinsic photoluminescence
respectively (λexc > 430 nm). Notably, enhanced emission for
(PL) property owing to the judicious choice of metal centers
[Cd2(L)(bpee)3(NO3)2]·2H2O·DMF·EtOH is observed due
and organic ligands and/or linkers that have been studied in a
detailed way over the years.1105−1107 Here we will depict some to parallel arrangement of monomer-like BODIPY planes by
of the selected examples for 2D MOFs with illustration. 14 Å.1116 Similarly, 8-hydroxyquinolinate and 1,4-bis(4-
2D MOFs based on d10 metal centers (Zn(II), Cd(II), or pyridyl)-2,3-diaza-1,3-butadiene based ligands are also pref-
Cu(I)) in combination with highly conjugated organic linkers erable to construct Zn(II)/Cd(II) 2D MOFs with emission in
have displayed linker-based PL within varied emissive 550−570 nm range.1117,1118
wavelength range. Wu and co-workers have reported (4,4)- Maji et al. reported a 1D to 2D to 3D interdigitated and
connected 2D MOFs, (H2NMe2)[Cd(TTAA)]·2H2O (chiral interwoven framework, [Cd(OPE-C8)(DMF)2(H2O)], based
with 2-fold right and left handed helical chains) and on a chromophoric bola-amphiphile oligo(p-phenyleneethyny-
(H 2 NMe 2 )[Cd(TTAA)]·H 2 O (achiral rectangular-grid) lene) (OPE) with dioxyoctyl side chains (H2OPE-C8) which
(H3TTAA = N,N′,N″-1,3,-5-triazine-2,4,6-triyltris(4-aminome- displayed solvent-directed bathochromic shifted emission from
thylbenzoic acid), with bright-blue emissions due to the cyan to green (Figure 198).1119 Furthermore, DFT calculations
fluorophore triazine-core ligand, TTAA (Figure 197a,b).1108 proved that the twisting of OPE rings in different solvent vapor
The emission wavelength is 432 nm (λexc = 318 nm) for both resulted in the shift. Temperature and solvent modulated
MOFs with 40.3/74% and 13.7/25.4% quantum yields at 298 fluorescence is also noted in [M(2,2′-bpda)(1,4-
and 77 K, respectively which suggested the presence of bdc)0.5(phen)]·0.5H2O (M = Ga/In; 2,2′-H2bpda = 2,2′-
temperature-dependent PL properties as well (Figure 197c,d). biphenyldicarboxylic acid).1120
Ghosh et al. revealed a homochiral 2D porous framework, Seco and co-workers revealed long lasting phosphorescence
[Cd(L)(H2O)]·3H2O (D-isosorbide dicarboxylate) with triple- (LLP) phenomenon which shows bright-blue emission upon
helical chains with blue emission at 402 nm (λexc = 291 nm) UV-light illumination, but after removal of it, a pale-green
and size-selective guest solvents H2O and MeOH over other afterglow persists for few seconds in a 2D sql net MOF [Zn(μ-
solvents.1109 LMCT-based green fluorescence at 497 nm (λexc 6-ani)2] (6-ani = 6-aminonicotinate).1121 A very short lifetimes
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single crystal of [Zn(μ-6-ani)2]. Later, similar reports are also

observed for [M(μ-2-ani)2] (M = Zn and Cd; 2-ani = 2-
aminonicotinate) and [Pb(2-ani)2].1122,1123 Computational
studies were carried out to validate the LLP process dictated
by LCCT mechanism in [Zn2(μ3-IA)2(H2O)4] and [Zn2(μ-
IA)2(DMF)]·H2O (IA2− = itaconate).1124 Other related
examples are provided for 2D MOFs.1125−1127
On the basis of Cu(I)-halide clusters, luminescent 2D MOFs
are also constructed. For example, two isostructural 2D MOFs,
[Cu2I2(L)2] (L = DABCO and piperazine), showed cluster
centered (CC) bright emission from yellow to red (λemi = 551
and 564 nm; 560 and 604 nm) at 295 and 77 K with very long
lifetimes of 609 and 420 μs at 77 K, respectively.1128 Similarly,
[{Cu(μ2-I)2Cu}{μ-PhS(CH2)3SPh}2] and [Cu4I4{μ-PhS-
(CH 2) 3 Ph} 2 ] (1,3-(PhS(CH2 ) 3 PhS) = bis(phenylthio)-
propane) with Cu2I2 and Cu4I4 clusters, respectively exhibited
emission at around 450 and 535 nm with long lifetimes in
microsecond range.1129 Highly red-shifted emissions in
[{Cu 2 (μ 2 -X) 2 } 2 (μ 4 -L)] (L = trans-Pt(PMe 3 ) 2 (C
CC6H4CN)2; X = Br, I) (λemi = 650/640 nm; quantum yield
∼30%) due to metal/halide to ligand charge transfer is
observed.1130 Mechanochemical luminescent properties in
Figure 198. (a) View of the asymmetric unit and (b) 3D structure Cu(4-pt)·G (G = toluene, ethanol; 4-pt = 5-(4-pyridyl)-
formed via interweaving of the 2D sheets in [Cd(OPE-C8)- tetrazole) upon immersion in different organic solvents is
(DMF)2(H2O)]. (c) Images showing the emission color changes reported with green (535 nm), yellow (552 nm), and orange
and corresponding wavelengths of emission when desolvated (615 nm) emission bands which changed to weak orange upon
[Cd(OPE-C8)(DMF)2(H2O)] was exposed to different solvent
vapors. (d) Corresponding photoluminescent profile showing the
strong grinding.1131
associated changes in emission. Adapted with permission from ref Guest inclusion with emissive properties within 2D MOFs is
1119. Copyright 2018 American Chemical Society. another interesting strategy to impart PL in these materials.
Jung et al. investigated C3 symmetric ligand-based 2D Zn-
of (6−8 ns) at 380−400 nm, while 0.70−1.11 s for long-lived MOFs, [Zn3L4(CH3CN)6](X)6 (L = 1,3,5-tris(isonicotinoyl-
components in addition to intermediate (0.19−0.43 s) over oxyethyl)cyanurate; X− = BF4− and ClO4−), which upon
the 425−600 nm range following LMCT and LCCT inclusion of fused aromatic hydrocarbons (FAHs), such as
mechanisms. In Figure 199, the microphotoluminescent anthracene, pyrene, perylene, phenanthrene, and naphthacene,
(micro-PL) images depicted the blue and green emission in into their hydrophobic nanochannels showed Förster reso-

Figure 199. (top) Crystal structure of [Zn(μ-6-ani)2]. (bottom) Micro-PL images of [Zn(μ-6-ani)2] at different excitation lines. Adapted with
permission from ref 1121. Copyright 2016 Royal Society of Chemistry.

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nance energy transfer (FRET) based emission from blue to (H2O)2] (Ln = Nd, Yb) with emissions at 888/892, 1055/
green region in monomeric or dimeric form (Figure 200).1132 1059, and 1329/1326 nm for Nd3+ compounds while at 997
nm for Yb3+ compound.1138 Introduction of filler type DMSO
(dimethyl sulfoxide) as coordinating solvent in chlorocyani-
late-based Yb/Er 2D MOFs also showed NIR emission with
high quantum yields (Figure 202).1139 Similar phenomenon is
also observed in mixed-metal 2D lanthanide structures.1136,1140

Figure 200. Crystal structure of [Zn3L4(CH3CN)6](BF4)6·5DCM·

3H2O: (a) Packing structure of 2D networks showing 1D nano-
channels and (b) top and side views of one [Zn3L2(CH3CN)6]6+ unit.
The included BF4− ions are represented as space-filling models. Solid-
state PL spectra (λexc = 365 nm), fluorescence microscopy images, Figure 202. Crystal structures of (a) [Yb2(ClCNAn)3(DMSO)4]·
and schematic structural representation of (c) anthracene (purple) DMSO (CN fragments appears as free C and N atoms as a
and anthracene@Zn-MOF (cyan) and (d) perylene (yellow) and consequence of the structural disorder involving the Cl and CN
perylene@Zn-MOF (cyan). Adapted with permission from ref 1132. substituents on the ligand) and (b) [Er2(ClCNAn)3(DMSO)6]. (c)
Copyright 2015 John Wiley & Sons. Steady-state emission spectra under 470 nm excitation of
[Yb2(ClCNAn)3(DMSO)4]·DMSO (purple) (λemi = 980 nm),
[YbEr(ClCNAn)3(DMSO)4]·DMSO (red) (λemi = 980 and 1530
Apart from these, a majority of lanthanide-based MOFs have nm) and [Er2(ClCNAn)3(DMSO)6] (blue) (λemi = 1530 nm) in the
been revealed to display PL property through strong f−f crystalline state. Adapted with permission from ref 1139. Copyright
transitions, which get sensitized when coordinated with highly 2019 Royal Society of Chemistry.
conjugated organic ligand due to antennae effect.1105,1107,1133
White-light emission (WLE) and near infrared (NIR) emission A series of mixed-metallic lanthanide 2D MOFs has been
have been mostly observed to be exhibited by these materials, investigated by Müller-Buschbaum et al. via in situ co-doping of
which are highly desirable in device applications. A (4,4)- lanthanide ions into [Bi2Cl6(pz)4] to form [Bi(2−x)LnxCl6(pz)-
connected 2D MOF, [La2(PDA)3(H2O)5] (PDA = pyridine-
4] (Ln = Sm, Eu, Tb, and Dy), which showed lanthanide-based
2,6-dicarboxylate), after doping with 1−2% Tb3+ and Eu3+
emission at room temperature, but on cooling to 77 K,
afforded isostructural complexes with tunable color change
bismuth−pyrazine MLCT related bluish-white phosphores-
from blue mixed with green (from Tb3+) and red (Eu3+) to
cence at 495 nm was revealed.1141 Several other examples
form near to ideal white light (0.33, 0.33) with CIE
based on Eu3+ and Tb3+ metal centers exhibiting red and green
coordinates (0.3269, 0.3123) and (0.3109, 0.3332) (Figure
emission, respectively, are also noted.1142−1151
201) and quantum yield = 6−7%.1134 Similar relevant studies
In addition, Wang and Lin et al. reported a luminescent Zr-
are well reported for other 2D MOFs.1135−1137
based 2D MOF substitute for lanthanide phosphors for white
Hong and co-workers reported NIR-emitting 2D lanthanide
light emitting diodes (WLED). Zr-TCBPE is a (4,4)-
MOFs based on 4-hydroxyquinoline-2-carboxylate (H2 hqc)
connected sql net based on [Zr6O4(OH)6(H2O)2(HCO2)6]
ligand [Nd(Hhqc) 3 (H 2 O)]·3H 2 O and [Ln(Hhqc)(ox)-
clusters and 4′,4′′,4′′′,4′′′′-(ethene-1,1,2,2-tetrayl)tetrakis-
([1,1′-biphenyl]-4-carboxylic acid) (H4TCBPE) ligand with
AIE feature and exhibits yellow emission at 560 nm (λexc = 450
nm) with lifetime of 2.6 ns. When it is combined with a GaInN
blue LED chip, it formed a 2D MOF-WLED with CIE
coordinates (0.37, 0.41) (Figure 203).1152
5.5. Photochromism and Thermochromism
Color changes upon exposure to external stimuli such as
photo-irradiation with UV or visible light and heat, often
reversible, generate photochromism and thermochromism
Figure 201. (a) 2D framework of [La2(PDA)3(H2O)5] and (b) CIE
phenomena, respectively. These emerging properties are
chromaticity diagram for [La2(PDA)3(H2O)5]:x%Tb3+, y%Eu3+ widely studied in MOFs with potential applications in
monitored under 312 nm ((a) x = 1.0, y = 2.0 and (b) x = 1.5, y = photonic and optoelectronic devices and photoswitchable
2.0). The insets are the optical photographs excited under 312 nm UV materials.1153 To develop photochromic materials, photoactive
lamps. Adapted with permission from ref 1134. Copyright 2012 Royal organic linkers such as electron deficient, redox-active viologen
Society of Chemistry. derivatives and naphthalene diimides (NDIs) are incorporated
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Figure 203. (a) Structures of the H4TCBPE ligand and Zr6 clusters. (b) Structure of Zr-TCBPE-MOF. (c) sql topology of Zr-TCBPE. (d) Ball-
and-stick model of the Zr6 cluster. (e) Emission spectra of Zr-TCBPE (orange line) and 450 nm LED (blue line) and the 2D MOF-WLED (black
line). (f) Coordinates of the MOF-WLED on CIE map (red square, Zr-TCBPE-MOF; yellow triangle, 450 nm LED; blue star, 2D MOF-WLED.
(g) Photo of the 2D MOF-WLED. Adapted with permission from ref 1152. Copyright 2017 John Wiley & Sons.

in 2D MOFs. Moreover, these 2D MOFs can behave as amine (bcbpy)0.5(pma)0.5(H2O)]·3H2O (H2bcbpy·2Cl = 1,1′-bis(3-
sensors via generation of cationic radicals accompanied by carboxylatobenzyl)-(4,4′-bipyridinium) dichloride; H4 pma =
electron transfer from electron-donor amine moieties to these pyromellitic acid), with colorless to blue change in UV light,
electron deficient centers. also showed vapochromic amine sensing with varied color
Li and Liang et al. revealed photochromic behavior for change mainly for NH3, ethylamine (EA), n-propylamine
[Cd2(ipbp)2(NO3)2]·2DMF in UV light and [Cd(ipbp)Br]· (PA), and n-butylamine (BA) and no change for DEA and
1.75H2O (H2ipbpBr = 1-(3,5-dicarboxyphenyl)-4,4′-bipyridi- triethylamine (TEA) (Figure 204c,d), as well as applied as
inkless and erasable prints.1155
nium bromide) in UV and visible light with color change from
Reversible photochromic and luminescence on/off switching
light yellow to brown and green, respectively.1154 Interestingly,
activity have been observed in Eu3+ and bipyridinium-based 2D
[Cd2(ipbp)2(NO3)2]·2DMF displayed vapochromic response MOFs due to electron transfer and intramolecular energy
toward diethyl amine (DEA) from light yellow to fuchsia transfer through good overlap of emission and photochromic
within 50 min that can be regained through MeOH wash absorption bands.1156,1157 [Zn(NDI-ATZ)(DMF)2] (NDI-
(Figure 204a, b). P hotoch romic 2D MOF, [Zn- ATZ = naphthalene diimide aminotetrazolate) based on NDI
moieties showed reversible photochromic effect from yellowish
to dark green in sunlight through radical generation, while its
thin film exhibited electrochromic features.1158 Recently,
several other relevant 2D MOFs based on these types of
moieties have been studied to exhibit photochromism.1159−1170
Tom et al. demonstrated reversible thermochromic
luminescence from yellow to red in a square grid MOF,
[ZnL2]·H2O (H2L = 2,3-butanedionebisisonicotinylhydra-
zone), over 40−90 °C associated with charge transfer on
cooling and thermal expansion for desorption of water
molecules on heating with 50 nm red-shift (Figure 205).157
For [Cu4I4(dmimpr)2] and [Cu6I6(dimb)3] (dmimpr = 1,3-
di(2-methyl-imidazol-1-yl)propane; dimb = 1,4-di(imidazol-1-
yl)butane), large red-shifts of 41 and 78 nm are displayed upon
cooling from 298 to 77 K, which resulted linear correlation of
Figure 204. (a) Crystal structure of [Cd2(ipbp)2(NO3)2]·2DMF. (b) excited state energies with Cu···Cu interactions.1171 Both
Its photochromic effect in UV light (top) and vapochromism toward thermochromic and mechanochromic properties resulted in
DEA vapor (bottom). (c) Crystal structure of [Zn-
(bcbpy)0.5(pma)0.5(H2O)]·3H2O. (d) Photochromic response to
blue-shift in [MeSi(3-Py)3]6(Cu6I6) (3-Py = 3-pyridyl) and
UV light and vapochromic sensing of different amines. (a,b) Adapted red-shift in [MeSi(3-Qy)3]6(Cu6I6) (3-Qy = 3-quinolyl),
with permission from ref 1154. Copyright 2017 Royal Society of owing to changes in secondary packing forces and Cu···Cu
Chemistry. (c,d) Adapted with permission from ref 1155. Copyright distance.1172 Demessence and co-workers investigated intrinsic
2019 Royal Society of Chemistry. triple emission in luminescent thermochromic Cu(I) thiolate
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5.6. Sensing
For environmental protection, luminescent MOFs endowed
with designable architectures and functionalities have con-
tributed a lot to the detection of varied harmful analytes
ranging from toxic metal ions, anions, small molecules, NEs or
NACs, pesticides, etc.1106,1107,1187,1188 Sensing can take place
by various modes involving colorimetric detection upon
analyte coordination or guest encapsulation, turn-on or turn-
off luminescence in the presence of a specific analyte due to
electrostatic interactions or also due to structural change.
Interactions between MOF and analyte is crucial that can take
place via clathration, reaction, coordination, etc.1188 In this
context, 2D MOFs are also efficient sensors for the detection
of varied analytes with selectivity which are discussed below.
5.6.1. Toxic Metal Ion and Anion Sensing. Ultra-high
sensitivity towards Pb2+ metal ion through fluorescence
quenching has been observed for a green emissive 2D MOF,
[Tb(L)(H2O)5] (H2L− = 3,5-dicarboxyphenol anion), with
limit of detection (LOD) to be 0.07 μg L−1.1189 The reason is
attributed to weak interaction between Pb2+ and Lewis basic
sites of phenolic oxygen in the MOF reducing the efficient
Figure 205. (a) Crystal structure of [ZnL2]·H2O. (b) Photographs of energy transfer from ligand to Tb3+ centers. Utilizing a pyridyl
letters C, U, S, A, and T using [ZnL2]·H2O at low temperature and 80 moiety appended 2D honeycomb framework, [Zn(ppvppa)-
°C within 2 s time interval. Thermochromism monitored by (c) (1,4-NDC)] (ppvppa = di-pyridin-2-yl-[4-(2-pyridin-4-yl-
fluorescence spectroscopy. Adapted with permission from ref 157.
vinyl)-phenyl]-amine; 1,4-H2NDC = 1,4-naphthalenedicarbox-
Copyright 2020 Royal Society of Chemistry.
ylic acid), Lang et al. displayed Hg2+ or MeHgI detection in
water (LOD = 0.02 ppm) via a turn-on process from pale-
orange (508 nm) to blue emission (494 nm) (Figure 206).1190
hexagonal sheet, [Cu(p-SPhCO2Me)], as a ratiometric The recognition of other metal ions, Cu2+, Hg2+, Fe3+, Cr3+,
Ag+, and Cd2+ by 2D MOF sensors are also found to be
temperature sensor over 93 to 503 K with bands at 460 nm
reported.1191−1199
(blue), 560 nm (green), and 740 nm (red), which upon
Discriminative colorimetric anion sensing by [Cu4(bpgxH2)-
temperature increment depicts decrease in intensity of all (bpy)4(NO3)2]·4H2O (bpgxH2 = α,α′-bis(N-pyroglutamyl)-p-
bands and bathochromic shift in red band. The intense xylene) with brick-orange color has been highlighted with fast
intensity at lower temperature is ascribed to the rigidified response time: beige (F−, ∼10 min), auburn (Cl−, ∼1 min),
framework, allowing rapid intersystem crossing process to wine red (Br−, ∼immediately), scarlet (I−, ∼30 s), amber
restrict the energy loss via non-radiative decay.1173 Other (SCN−, ∼1 min), light sea green (PF6−, ∼10 min), moss green
interesting temperature sensors based on Cu−I clusters, (ClO4−, ∼20 min), yellow green (BF4−, ∼15 min), turquoise
heterometallic lanthanide centers, and other related systems (NO2−, ∼5 min), bottle green (WO42−, ∼40 min), and indigo
are also reported.851,1174−1186 (MoO42−, ∼40 min).1200 Lang and co-workers also demon-

Figure 206. (a) View of 2D MOF [Zn(ppvppa)(1,4-NDC)]. (b) Its emission spectra with increasing concentration of Hg2+ aqueous solution. (c)
Color of the suspensions of 2D MOF with different metal ions under UV light. Adapted with permission form ref 1190. Copyright 2016 Royal
Society of Chemistry.

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strated turn-of f sensing of oxoanions such as dichromate with 75% and 86% quenching efficiency, respectively, via
(Cr2O72−) and chromate (CrO42−) with LOD of 1.39 and 0.09 host−guest π···π stacking interactions (Figure 208).1238 Similar
ppb, respectively, attributed to energy transfer process.1201 approach is also observed in [Cd3(TTPB)2(H2O)6]·6DMF
Other reports on oxoanion detection are also investigated by (H3TTPB = 1,3,5-tri(4-(2H-tetrazol-5-yl)phenoxy)benzene)
few other 2D MOFs.1202−1211 Several other 2D MOFs for for NACs detection.849
dual-responsive cation and anion sensing have been reported in
the literature as well.1212−1225
5.6.2. Small Molecule and Humidity Sensing. Solvents
and VOCs considered as small molecules are also investigated
for sensing purposes. As an example, blue-emissive 2D MOF,
[Cd(e,a-cis-1,4-chdc)(5,5′-dmb)]·H2O·CH3OH (1,4-chdc =
1,4-cyclohexanedicarboxylato), dispersed in acetone displayed
turn-on sensing of acetonitrile (LOD = 53 μM) over other
organic solvents.1226 Zhao and co-workers demonstrated an
AIE fluorogen tetraphenylethene (TPE)-based 2D MOF,
[Zn4O(DPEB)3(H2O)3]·12DEF·8H2O (DPEB = 4,4′-(2,2-
diphenylethene-1,1-diyl)dibenzoate), for turn-on detection of
VOCs with the noticeable intensity change and peak shifts due
to conformational variation of hanging phenyl rings (Figure
207).1227 Highest bathochromic shift of 18 nm has been

Figure 208. (a) Perspective view of the starfish array of [Zn1.5(L)-

(H2O)]·1.5benzene. (b) Schematic visualization of supramolecular
wire effect with cylindrical units of the π-stacked L moiety in a
framework along the c-axis (orange and blue color indicates two
different 2D sheets). (c) Quenching profile of guest-free 2D MOF by
nitrobenzene. Adapted with permission from ref 1238. Copyright
2013 American Chemical Society.

Naked eye trinitrotoluene (TNT) detection along with

unique detection of trinitrophenol (TNP), NB, and 1,3-
Figure 207. (a) Crystal structure of [Zn4O(DPEB)3(H2O)3]·12DEF·
8H2O. (b) Relationship of quantum yield versus wavelength shift of
dinitrobenzene (1,3-DNB) based on shift in emission spectra is
this 2D MOF in the presence of different VOCs. Adapted with depicted by [Cd2Cl(H2O)(L)]·4.5DMA (H3L = 4,4′,4′′-
permission from ref 1227. Copyright 2014 American Chemical ((2,2′,2′′-(nitrilotris(methylene))tris(1H-benzo[d]imidazole-
Society. 2,1-diyl))tris(methylene)) tribenzoic acid) decorated with
aromatic π-rings and Lewis basic nitrogen centers from
tripodal ligand.1239 Similarly, Bharadwaj et al. reported
observed for benzene and high quantum yield of 49%, with [Zn3(L)3(urotropine)2]·2DMF·3H2O based on 6-(4-carbox-
hypsochromic shift of 28 nm for mesitylene. For electrically yphenyl)-2-naphthoic acid (H2L) and urotropine (hxl top-
conductive Cu(II) 2D MOFs, Dincǎ et al. demonstrated ology) for TNP sensing at 1.93 ppm level in DMF with Stern−
chemiresistive sensing of VOCs through linear discriminant Volmer constant (KSV) value 5.1 × 104 M−1.1240 Mandal et al.
analysis and ambient CO2 with RH sensitivity (400−2500 demonstrated the discriminative detection of NACs at ppm
ppm).1228,1229 A few more reports on solvents, VOCs, and gas level in aqueous medium by structurally diversified 2D hcb
sensing appeared in the literature.188,1195,1196,1205,1211,1230−1234 MOFs, [Zn2(tpbn)(ndc)2] and [Zn2(tphn)(ndc)2]·4H2O,
A semiconductive gyroidal anionic Pb−S network of based on flexible bis(tridentate)polypyridyl ligands, tpbn =
[Pb 3 OH 0.5 (HTT)] 1.5− (HTT = 2,3,6,7,10,11-hexakis- N,N′,N″,N‴-tetrakis(2-pyridylmethyl)-1,4-diaminobutane and
(butyrylthio)triphenylene) with polarizable Pb-dithiolene link- tphn = N,N′,N″,N‴-tetrakis(2-pyridylmethyl)-1,6-diaminohex-
ages exhibited chemiresistive humidity sensing over 5−100% ane).1241
RH.1235 Additionally, 3-thiophenemalonic acid (TMA) based Bis-9,10-(pyridine-4-yl)-anthracene (BA) has been utilized
2D MOFs also served as humidity sensors.1236,1237 to construct a blue-emissive 2D (4,4)-connected Cd(II) MOF,
5.6.3. Nitroexplosives/Nitroaromatics, Amines, Pesti- [Cd(μ2-BA)2(ClO4)2]·DCM with ClO4− ion induced structure
cides, and Antibiotics Sensing. Highly conjugated, bearing pore size of 11.2 × 11.2 Å2 to encapsulate desired
fluorophore appended ligands and/or free Lewis basic nitrogen guest analytes (Figure 209a).1242 This resulted into potential
rich moieties such as pyridyl and amine have been adopted to sensitivity with turn-of f response towards chloroaromatic
impart efficient PL recognition sites in 2D MOFs through π···π herbicide simazine (6-chloro-N,N′-diethyl-1,3,5-triazine-2,4-
and electronic interactions with electron deficient Lewis acidic diamine, SEM) (LOD: 122 ppb) and 2,4,6-trichloroanisole
NEs/NACs, allowing resonance energy transfer (RET) and (TCA) (LOD: 16.5 ppb) as well as TNP (LOD: 15.6 ppb)
photoinduced electron transfer (PET). Ghosh et al. revealed a (Figure 209b) in solution phase and TCA (266 ppb) and
highly luminescent π-electron rich 2D starfish array [Zn1.5(L)- trinitrobenzene (TNB) (LOD: 74 ppt) in gas phase.
(H2O)]·1.5benzene (L = 4,4′,4′′-(benzene-1,3,5-triyltris- A reversible turn-on Cu(I) sensor for aniline, [Cu6(μ3-I)6(μ3-
(oxy))tribenzoate) showing “supramolecular wire ef fect” with PTAO)2] (PTAO = 1,3,5-triaza-7-phosphaadamantane-7-
hexagonal pores for vapor phase sensing of aliphatic and oxide) with cage-like aminophosphine units and kgd topology
aromatic NEs such as nitromethane and nitrobenzene (NB) revealed visual naked eye detection from yellow-green to
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MOFs have been widely explored which are capable of

detecting different categories of harmful analytes involving
NACs/NEs, metal ions, and anions with moderate to good
sensitivity and selectivity.1270−1292
5.6.4. Amino Acid and DNA Sensing. Homochiral 2D
Zn-MOFs, [Zn(RR-PCCHC)2] (RR-PCCHC = (1R,2R)-2-
(pyridine-4-ylcarbamoyl cyclohexanecarboxylic acid), with
DNA-like right-handed double-helix and [Zn(UDP)(bpy)-
(H2O)2][Zn2(UDP)(bpy)(H2O)6]·6H2O (UDP = uridine-5′-
Figure 209. (a) Schematic illustration of encapsulation of simazine, diphosphate) displayed amino acid sensing of aspartic acid
TNP, and TCA inside crystal structure of [Cd(μ2-BA)2(ClO4)2]· (LOD = 13.31 ppm) and tryptophan (LOD = 50 μM),
DCM. (b) Fluorescence sensing of TNP in acetonitrile. Inset: Stern− respectively.1293,1294 Fluorescence quenching of a dye-labelled
Volmer plot for TNP and corresponding UV-light illuminated cuvette ssDNA probe by [Ba2(L)(H2O)]·0.5DMF·3H2O (H4L =
images depicting turn-of f response. Adapted with permission from ref bis(3,5-dicarboxy-phenyl)terephthalamide) has been utilized
1242. Copyright 2019 American Chemical Society.
for an activity assay of deoxyribonuclease I (DNase I).1295
Similar studies on HIV-1 ds-DNA sequences and other
orange in liquid and vapor phase at 0.26 and 0.065 ppb level,
biomolecules sensing are also noted.1296−1298
respectively, through charge transfer process.1243 A dual turn-
off sensor [Zn2(2-MI)(ndc)2(DMF)] (2-MI = 2-methylimida- 5.7. Proton Conductivity
zole) showed LOD of 58 and 60 nM for TNP and 2,6- The recent advances achieved in the design of proton
dichloro-4-nitroaniline (2,6-DCNA, a broad-spectrum pesti- conductive MOFs have been critically reviewed and discussed
cide used for crop protection) in water, respectively.1244 An by several groups.1299−1305 The proton conductivity in 2D
excellent visual colorimetric detection of polar solvents, MOFs was investigated as early as 1979 by Kanda et al. The
monohalobenzenes and NACs in vapor phase, has been 2D MOF [Cu(R-dtoa)] (R-dtoa = N,N′-bis(2-hydroxyethyl)-
demonstrated by Konar et al. by a (4,4)net to 3D interdigitated dithiooximide) was investigated for its electrical and proton
framework, [Cu(L)(I)]2·2DMF·MeCN (L = 4′-(4-methox- conducting properties.1306 Later, the same group measured the
yphenyl)-4,2′:6′,4″-terpyridine), through SCSC transforma- room-temperature proton conductivity of [Cu(H2 dtoa)]
tion (Figure 210).1245 Host−guest interactions were supported under the RH of 75% from Cole−Cole plot analysis to be
10−6 S cm−1.1307 Moreover, hydrogen doping of (HOC2H4)2
dtoaCu displayed nine orders of linear increment in magnitude
of proton conductivity.1308
For an oxalate-based 2D MOF (NH4)2(adp)[Zn2(ox)3]·
3H2O (adp = adipic acid), Kitagawa and co-workers reported
the conductivity to be 8 × 10−3 S cm−1 at 25 °C and 98%
RH.1309,1310 Interestingly, the number of water molecules in
lattice has pronounced influence on the proton conductivity
from ∼10−12 S cm−1 for 1H2O to ∼10−2 S cm−1 for 3H2O.1311
Feng and co-workers reported [In(imdcH)(ox)](NH4)-
(H2O)1.5 (imdcH = 4,5-imidazolate) composed of three
types of 4-connected rings with ABCD stacking mode and
Figure 210. (a) Schematic representation for synthesis of [Cu(L)- two types of hydrophilic proton tunnels to provide proton
(I)]2·2DMF·MeCN and (b) SCSC visible color changes for solvents conductivity of 0.82 × 10−3 S cm−1 at 23.5 °C and 98.6%
and monohalobenzenes (top), amines and NACs (bottom). Adapted RH.1312
with permission from ref 1245. Copyright 2015 American Chemical Anisotropic proton conductivity was observed in
Society. [Cu2(Htzehp)2(bpy)]·3H2O (H3tzehp = N-[2-(1H-tetrazol-
5-yl)ethyl]-L-hydroxyproline). The Htzehp ligand bonded to
by blue-shift in fluorescence emission as well as high selectivity Cu(II) atoms are shown in Figure 211a,b. This material loses
for DEA and TNP reflected in quenching efficiency and the crystal hydrates in an SCS manner. The anisotropic proton
Stern−Volmer constant value. Similar study using the same conductivity of σ[100]/σ[010] measured in a single crystal of
framework to encapsulate CHCl3, DCM, and CCl4 via SCSC the trihydrate was as high as two orders of magnitude (Figure
manner and selectively detect aniline is also reported later.1246 211c). The proton conductivity of 1.43 × 10−3 S cm−1 at 80 °C
Other related 2D MOF sensors for NEs/NACs and pesticides and 95% RH observed here highlights the relationship between
detection are also reported in the literature.1181,1247−1265 the proton conductivity and the structure.1313
Antibiotics with nitro groups such as nitrofurazone (NZF), By isomorphous ligand replacement and doping with 1H-
nitrofurantoin (NFT), or furazolidone (FZD) have been also 1,2,4-triazole, the proton conductivity in a 2D MOF, β-
detected at ppb and ppm level by 2D MOFs.1204,1208,1266−1268 PCMOF2 (Figure 212a,b), has been increased to two orders of
For [Zn(L)(H2O)]·H2O (H2L = 5-(2-methylpyridin-4-yl)- magnitude to over 10−1 S cm−1 at 85 °C and 90% RH (Figure
isophthalic acid) with blue emission, Wang et al. reported 212c).1314
multidetection of Cr3+ (LOD = 2.44 μM), CrO42−(LOD = In the bimetallic oxalate 2D MOFs {NH(prol)3}[M(II)Cr-
4.80 μM), Cr2O72− (LOD = 3.53 μM), and 4-nitrophenol (4- (III)(ox)3]·3H2O (M = Mn, Fe, Co and NH(prol)3 =
NP; LOD = 3.74 μM) owing to competitive absorption and ammonium tri(3-hydroxypropyl) cation) have been designed
electronic interactions between the host MOF and analy- to exhibit both ferromagnetic and proton conducting proper-
tes.1269 In addition, many multifunctional luminescent 2D ties.1315 Ferromagnetic ordering and proton conductivity was
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workers.1324 A few 2D MOFs have been investigated as proton

conducting materials.831,1325−1338
5.8. Electrical Conductivity
MOFs are usually considered as insulators with conductivity
less than 10−10 S cm−1 due to unavailability of low-energy
charge transport pathways and free charge carriers.1339 Several
2D MOFs have been recently demonstrated to have excellent
electrical conductivity and high charge mobility. 2D conductive
MOFs have potential applications as chemiresistive sensors,
electrode materials, electrocatalysts, electronic devices, elec-
trical energy storage, and spin-polarized transport materi-
als.890,1340−1344 The design strategies to synthesize conducting
2D MOFs involve the use of the ligands shown in Figure
213.1342
Figure 211. (a) Coordination environment of Cu(II) and Htzehp2−
In 2012 Yaghi et al. reported the single crystals of a 2D
and bpy ligands. (b) 2D framework in the MOF. Only selected atoms Cu(II) MOF containing conjugated tricatecholate,
are shown. (c) Plots of ln(σT) vs 1000/T for the single crystals of the 2,3,6,7,10,11-hexahydroxytriphenylene, to exhibit electrical
MOF at 95% RH measured along the [100] and [010] directions. conductivity of 1.8−2.1 × 10−1 S cm−1 and charge storage
Adapted with permission from ref 1313. Copyright 2017 American capacity of 284 C g−1 (80 mA h g−1).1345
Chemical Society. Dincǎ and co-workers reported a 2D Ni(II) MOF,
[Ni3(HITP)2], shown in Figure 214a to display a very high
also observed in a series of similar bimetallic 2D oxalate conductivity of bulk (pellet and film of 2 and 40 S cm−1,
framework materials,1316 whereas proton conductivity can be respectively (Figure 214b). 1 346 The Cu(II) MOF,
controlled by hydrophilicity of the cations in another oxalate [Cu3(HITP)2], which displays a bulk (pellet, two-point-
MOF.1317 Inherent proton conductivity by neutral 2D MOF probe) conductivity of 0.2 S cm−1, is able to detect sub-ppm
material [Zn(H2PO4)2(Tzh)2] (Tzh = 1,2,4-triazole) was levels of ammonia vapor.1347 The measurements on single
reported by Kitagawa et al.1318 His laboratory also demon- crystal rods of these Cu(II) and Ni(II) 2D MOFs exhibit
strated the formation of a glass from the corresponding Cd(II) conductivities up to 150 S cm−1.1348,1349 A series of such 2D
MOF [Cd(H2PO4)2(Tzh)2]. This glassy state has enhanced MOFs have been used as sensors for a number of volatile
proton conductivity and increased dielectric constant, with organic molecules.1228,1350 Computational calculations show
more flexibility and transparency.1319 that these [M3(HITP)2] sheets exhibit Kagomé-lattice pattern
A 2D MOF made up of 3d−4f metal ions [Co(III)La(III)- and the properties vary from semiconducting for Ni(II) to
(notpH)(H2O)6]ClO4·5H2O undergoes a phase transition metallic for Cu(II).1351
above 45 °C and 93% RH to [H3O][CoLa(notp)(H2O)4]· Nanosheets (<10 nm) of 2D MOFs derived from
ClO4·3H2O (notpH6 = 1,4,7-triazacyclononane-1,4,7-triyl-tris- hexaminobenzene ligands with Ni(II), Cu(II), and Co(II)
(methylenephosphonic acid) or C9H18N3(PO3H2)3). The have been successfully made by liquid−liquid and air−liquid
transition is accompanied by the release of the proton from interfacial reactions. The low conductivity observed has been
intralayer to interlayer, and thus the proton conductivity of the attributed to crystal defects and grain boundaries.1352 On the
material is increased by one order of magnitude.1320 Further, contrary, Dincǎ and co-workers showed that under controlled
the SCSC structural transformation in [Co(III)Ca(II)- conditions, these 2D MOFs as bulk materials have
(notpH2)(H2O)2]ClO4·nH2O was shown to be humidity conductivities exceeding 800 S m−1.1353
dependent between 2H2O and 4H2O. This is accompanied Bis(ditholene) ligand based 2D MOFs have been inves-
by a drastic change in the proton conductivity, thus making tigated for their electrical conducting properties.1354−1357 Of
this a promising humidity sensor.1321 Schröder and co-workers these, the nanorods of the Ni(II) 2D MOF derived from the
also investigated phosphonate-based hexagonal layered 2D perthiolated coronene ligand display an electrical conductivity
MOFs with enhanced proton conductivity values.1322,1323 of ∼9 S cm−1 at 300 K and a weak semiconductor-like
Proton conductivity is also shown to occur via highly ordered dependence. Seebeck coefficient of 47.0 mV K−1 and an
water molecules in a 2D MOF reported by Shimizu and co- extremely low thermal conductivity of 0.2 W m−1 K−1 resulted

Figure 212. (a) Space-filling structure of β-PCMOF2 with its 1D proton conduction channel illustrated with an arrow and the schematic
illustration of isomorphous replacement. (b) 2D layout of β-PCMOF2 where the pores are impregnated with heterocycles (teal pentagons). (c)
Plot of log conductivity versus 1/T. Reproduced with permission from ref 1314. Copyright 2017 American Chemical Society.

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Figure 213. Various ligands used to construct electrically conductive 2D MOFs. Adapted with permission from ref 1342. Copyright 2020 John
Wiley & Sons.

Figure 215. Schematic diagram showing the electrical conductivity

and magnetic ordering in a 2D MOF due to the presence of radical
Figure 214. (a) Chemical structure of [Ni3(HITP)2] and the
ligand. Reproduced with permission from ref 1362. Copyright 2017
diradical linkage. (b) Variable-temperature van der Pauw conductivity
American Chemical Society.
measurement on a ∼500 nm thick film on quartz. Adapted with
permission from ref 1346. Copyright 2014 American Chemical
Society. Magnetic measurements of this reduced form reveal the
presence of dominant intralayer metal−organic radical
in a thermoelectricity of 0.003 at 300 K. All of these properties coupling resulted in a magnetically ordered phase below Tc
make this MOF have an interesting conducting material with = 105 K. This is one of the highest reported ordering
p-type thermoelectric performance.1358 Benzenehexathiolate temperatures for a MOF. In addition to the high critical
lamellar framework based on Ag−Ag and Ag−S−Ag infinite temperature, the new MOF also exhibits magnetic hysteresis
chains and its thin film exhibited very high electrical up to 100 K. Further, the electrical conductivity values are up
conductivity of 250 S cm−1 at 300 K.1359 Recently, the to σ = 5.1(3) × 10−4 S cm−1 with Ea = 0.34(1) eV.1362
compressed powder sample of a Cu(II) bis(diselenolene) 2D The electrical conductivity of a La(III) 2D MOF containing
MOF synthesized from benzenehexaselenol showed an semiquinone radical anion, anthraquinone-1,5-disulfonate
impressive 110 S cm−1 at 300 K by Zhu and co-workers. anion, was measured in a single crystal at room temperature
The band structure calculation and ultraviolet photoelectron to be 3 × 10−3 S cm−1. The conductivity is attributed to the
spectroscopy (UPS) experiment reveal the metallic character π···π stackings in the layered structure.1363 Doping of 7,7,8,8-
of this MOF.1360 Also, they revealed electrical conductive and tetracyanoquinodimethane (TCNQ) in the films of a 2D MOF
glassy magnetic properties in a Co-triphenylenehexaselenol 2D indeed increased the conductivity by 3-fold.1364 A redox active
MOF.1361 2D MOF based on Mo2(ina)4 (ina = isonicotinate) clusters is
A quinoid-based 2D MOF simultaneously exhibits both high reported to show conductivity via through framework charge
magnetic ordering temperatures and high electrical conductiv- transfer pathway.1365 Metallic and conductive properties in
ity (Figure 215). The oxidized compound, (Me2NH2)2[Fe2L3]· honeycomb-based 2D MOFs were investigated using first-
2H2O·6DMF (LH2 = 2,5-dichloro-3,6-dihydroxo-1,4-benzo- principles calculations.1366−1368
quinone), showed magnetic ordering below 80 K in its solvated A layer-by-layer assembly was achieved to fabricate highly
form. It also exhibits electrical conductivity values up to σ = crystalline and oriented thin films of a 2D-MOF,
1.4(7) × 10−2 S cm−1 (Ea = 0.26(1) cm−1) and 1.0(3) × 10−3 S [Cu3(HHTP)2], with tunable thicknesses on the ferromagnetic
cm−1 (Ea = 0.19(1) cm−1) in its solvated and desolvated forms, electrode, La0.67Sr0.33MnO3 (LSMO). The magnetoresistance
respectively. When soaked in a DMF solution of Cp2Co, it (MR) of the LSMO/[Cu3(HHTP)2]/Co organic spin valves
undergoes one-electron reduction to give (Cp2Co)1.43- (OSVs) reaches up to 25% at 10 K. The MR can be retained
(Me2NH2)1.57[Fe2L3]·4.9DMF in an SCSC manner with the with good film thickness adaptability varied from 30 to 100 nm
trianionic framework is formulated as [Fe(III)2(L3•−)3]3−. up to 200 K. The electrical conductivity of the [Cu3(HHTP)2]
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material was estimated to be 0.29 S cm−1. Thus, this could cycling stability.1397 Since then, several 2D MOFs have been
serve as a possible platform for the development of 2D MOF- investigated for both anode and cathode materials for LIB
based spintronics.1369 Kitagawa et al. recently investigated applications.1398−1408
[Cu3(HHTP)(THQ)] (THQ = tetrahydroxy-1,4-quinone) Dincǎ et al. showed that the highly electrically conductive
with modulated conductivity of 2.53 × 10−5 S cm−1 and 2D MOF, [Ni3(HITP)2], can serve as a single active electrode
activation energy of 0.30 eV and its nanofilm on an Au in electrical double layer capacitors without conductive
interdigital electrode displayed chemiresistive NH3 vapor additives or other binders. The MOF-based device shows
sensing at ppm level.1370 Chloraniliate ditopic linkers have very high volumetric capacitance values with the capacity
been used to construct conductive 2D layered mixed-valence retention greater than 90% over 10 000 cycles.1409 Another
MOFs due to redox non-innocent behavior.1371 conducting 2D MOF based on hexaaminobenzene (HAB)
Banerjee and co-workers measured the electrical conductiv- showing the bulk electrical conductivity of 1.57 S cm−1 exhibits
ity of the two supramolecular isomers, namely, the rod-shaped high rate capability of 214 mA h g−1 within 7 min or 152 mAh
(Me2NH2)[In(ip)2]·2H2O and cubic crystals of (Me2NH2)- g−1 in 45 s as a promising electrode material for sodium-ion
[In(ip)2]·DMF. The presence of π···π stacking in the cubic storage.1410 The corresponding Ni-MOF also shows a stable
crystals facilitate the high carrier mobility (4.6 × 10−3 cm2 V−1 cycling performance and a high specific capacity of 155 mA h
S−1 at VG = −40 V), whereas the lack of π···π stacking in the g−1 as a cathode material for LIBs.1411 Using first principle
rod-shaped crystal shows no charge carrier mobility.1372 The
calculations, another electrically conducting 2D MOF Cu-
electrical conductivity of a Ni(II) 2D MOF based on
benzenehexathial has been demonstrated to be a promising
tetraaza[14]annulene-linked ligand, TAA can be changed
sulphur host material for high-performance Li−S batteries.1412
from an insulater to a conductive materials (electrical
By availing a conductive 2D Mn-hexaaminobenzene-based
conductivity of 0.01 S cm−1) by chemical oxidation by iodine.
This partially oxided MOF is also paramagnetic, with weak (Mn-HAB) MOF along with an amorphous Li−S layer, a 3D
antiferromagnetic coupling due to the presence of organic sandwich Li−S cathodic material with theoretical gravimetric
radicals of oxidized ligands and high-spin Ni(II) sites of the capacity of 825 Wh/kg and a volumetric energy density of
missing-linker defects.1373 The electrical conductivity and 1652 Wh/L has been designed by Wang et al.1413 The
other electrochemical measurements have been made in a theoretical study of the pristine MOF was revealed by the same
few 2D MOFs as a routine characterization.1158,1374−1384 The group earlier.1414
theoretical aspects of the electronic and conductive properties Because of the high-rate performance, cost, and safety,
of 2D MOFs have been reviewed recently.1385 rechargeable aqueous zinc batteries are gaining importance
recently. Stoddart and co-workers investigated the conductive
5.9. Battery Applications and Supercapacitors
2D-MOF, [Cu3(HHTP)2], as a zinc battery cathode. Hydrated
In recent years, MOFs have been explored extensively for Zn(II) ions are successfully inserted into the 1D channels
electrochemical energy storage materials, especially in directly into the MOF. High diffusion rate and low interfacial
rechargeable batteries, supercapacitors, and as electrocata- resistance enable the MOF cathode to follow the intercalation
lysts.11,16,1386−1392 They have also been a source as templates pseudo-capacitance mechanism. This material exhibits a high
and precursors to generate carbon/metal oxides/metal reversible capacity of 228 mAh g−1 at 50 mA g−1. At a high
sulfides.1386,1387,1389 Electrical conducting 2D MOFs, com- current density of 4000 mA g−1 (∼18 C), 75% of the initial
bined with their ultrathin characteristics, processability, high capacity is maintained after 500 cycles.1415
surface area, and charge transfer surface redox properties, are Electrochemical properties of several 2D MOFs have been
suitable for electrochemical energy storage applications.1342 reported.156,1416−1421 For example, Long et al. recently
Because of the presence of weak interactions between the reported two iron−semiquinoid 2D MOFs, (H2NMe2)2-
layers, these 2D MOFs have been successfully exfoliated into Fe2(Cl2 dhbq)3 and (H2NMe2)4Fe3(Cl2dhbq)3(SO4)2 (Cl2
nanosheets and films exhibiting catalytic performance with dhbqn− = deprotonated 2,5-dichloro-3,6-dihydroxybenzoqui-
good stability and durability.
none), which displayed metal and ligand-centered electro-
In 2012, redox active 2D layer structures
chemical capacities up to 195 mAh g−1. These were also
K2.5[(VO)2(HPO4)1.5(PO4)0.5(C2O4)], Na2[(VO)2(HPO4)2
utilized as cathode to device lithium-ion storage materials.1420
(C2O4)], and KLi[(VO)2(HPO4)2(C2O4)] were investigated
by Vittal et al. as 4 V cathode materials for lithium ion batteries The supercapacitor and electrocatalytic properties have been
(LIBs). 1 3 9 3 An other similar layered compoun d, investigated in a number of redox active 2D MOFs.1422−1432
Li2[(VO)2(HPO4)2(C2O4)], synthesized by the same group One strategy to make metal, metal oxide, metal sulfide, and
has highly reversible Li insertion and extraction at 3.9 V. This metal selenide nanocrystals with controlled morphology is by
material shows a stable reversible capacity of 80 mA h g−1 at a converting the nano-2D MOFs by various methods. These
current rate of 0.1 C.1394 have been used for fabricating energy storage materi-
The redox active properties of anthraquinone-2,7-dicarbox- als.1433−1439 As an example, utilizing a facile bottom-up
ylate (2,7-AQDC) and Cu(II) has been successfully exploited approach, 2D cyanide-bridged Ni-MOF precursor has been
in a Kagomé lattice framework (kgm) compound [Cu(2,7- synthesized by the coprecipitation method involving NiCl2·
AQDC)(DMF)]·DMF in the voltage window of 4.0−1.7 V. A 6H2O, sodium dodecyl sulfate (SDS), and K2[Ni(CN)4]·
specific capacity of ∼105 mA h−1 has been stabilized for 50 xH2O. Then subsequent calcination in the presence of sulfur
cycles for this cathode material.1395,1396 Recently, a benzoqui- and selenium powder, respectively, produced carbon coated
noid-based MOF, [Cu-THQ] (THQ = tetrahydroxy-1,4- NiS and NiSe2 nanoplates due to sulfurization and selenization
quinone), has been found to be an excellent LIB cathode processes.1433 These two nanoforms display potential Li/Na
material and show a high reversible capacity of 387 mA h g−1, a ion storage capacity required for developing advanced anode
large specific energy density of 775 Wh k g−1, and a good materials.
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5.10. Electrocatalysts, HER, and OER electrocatalytic OER activities.1463 Several other studies on
The 3D MOFs are in general have low conductivity and mass fabricated hybrid 2D MOFs as efficient alkaline OER active
permeability and hence they have limited use as electro- electrocatalysts have been demonstrated by other groups as
catalysts. On the contrary, the porous 2D MOFs are well.1464−1469
advantageous in electrochemical applications, especially as Biradha et al. constructed 2D MOFs of Ni(II), Co(II), and
electrocatalysts with improved mass and electron transfer Cu(II) using electron rich bis(5-azabenzimidazole) derivatives
ability.1440−1445 They also have highly accessible active sites for and 1,4-benzenedicarboxylates. These MOFs were found to be
electrocatalysis as well as the ease of exfoliation into effective electrocatalysts for OER in alkaline media (pH = 13)
nanosheets in the modular synthesis using the bottom-up with exceptional cyclic stability over 1000 cycles. The
approach.1392,1446−1453 overpotential required for the production of 1 mA cm−2
The proton conductivity of the 2D MOF, [Cu(dtoa)] (dtoa current density for Ni(II) MOF was found to be the lowest
= N,N′-bis(2-hydroxyethyl)dithiooxamidate), was explored by (370 mV).1470
Kitagawa et al.1307,1454 The same MOF is a good catalyst for A NiFe-based 2D MOF, [Ni0.8Fe0.2(ndc)(H2O)4], has been
the electrooxidation of ethanol to acetaldehyde. The oxidation demonstrated to be a superior electrocatalytic performance
potential and current density are comparable with the Pt-based towards OER with a small overpotential of 240 mV at 10 mA
catalysts.1455 cm−2 and robust operation for 20 000 s with no detectable
Highly efficient low-cost electrocatalysts for the cathodic activity decay. The TOF of the electrode is 3.8 s−1 at an
oxygen reduction reaction (ORR) remain elusive for both overpotential of 400 mV. Moreover, it is also a promising
hydrogen and methanol fuel cells.1456 A highly intrinsically electrode for HER and water splitting.1471 Other bimetallic
conducting nanoporous 2D MOF, [Ni3(HITP)2], developed semiconductive 2D MOFs have been investigated for methanol
by Dincǎ’s laboratory, has been investigated to be a tunable oxidation and water splitting.1472,1473 A cobalt/N-doped
oxygen reduction electrocatalyst in alkaline solution. The carbon 2D composite derived from pyrolysis of [Co(ndc)-
primary product is the two-electron reduction to peroxide, (H2O)4] also exhibited comparable HER activity as observed
HO2− (88% selectivity), although the four-electron reduction in commercial Pt/C catalyst with overpotential of 103 mV (vs
to H2O is also observed. The rate-limiting step in the catalytic RHE) at 10 mA cm −2 in alkaline medium.1474 Two
cycle appears to be superoxide, O2−, formation.1457 Moreover, bis(dithiolene) based cobalt sheet-like MOFs, [NaCo(L)] (L
carbon dioxide reduction reaction (CRR) following proton- was derived from benzene hexathiolate or triphenylene-
coupled multi-electron transfer pathway with the CO2̇− as the 2,3,6,7,10,11-hexathiolate), were shown to exhibit HER
key intermediate has been demonstrated by 2D MOF activities.1475 A few reports appeared on HER using extended
nanosheets.1458,1459 bis(dithiolene) and mixed dithiolene-imine based 2D
One of the major thrusts in this area is towards the MOFs.1476−1478 A (3,4)-connected [Ni2(1,4-bdc)2(DABCO)]
electrochemical reduction of nitrogen (nitrogen reduction 2D MOF is converted into a N-doped Ni@carbon nano-
reaction, NRR) at ambient conditions for the industrial composite by pyrolysis, which serves as an efficient catalyst for
synthesis of ammonia. DFT computational calculations reveal the OER.1479 Other reactions such as electrocatalytic oxidation
that a bis(dithiolene) based osmium containing 2D MOF of urea, nitrite, ascorbic acid, and reduced glutathione are also
exhibits excellent catalytic performance for NRR due to its low studied by 2D MOFs.1480−1484
overpotential, 0.31 V and high selectivity.1460 Similarly, 5.11. Catalysis for Organic Synthesis
another molybdenum-based 2D MOF was investigated
computationally.1461 MOFs decorated with uniform and confined catalytic sites
Zhang et al. successfully removed the pillars from a pillared such as Lewis or Brønsted acid open metal sites and Lewis
layer 3D MOF (H3O)2[Co6O(dhbdc)2(H2dhbdc)2(EtOH)4]· basic functional sites have aroused the importance of these
2EtOH (H2dhbdc = 2,3-dihydroxy1,4-benzenedicarboxylic material in the form of catalysts for heterogeneous catalytic
acid) by in situ electrochemical oxidation of the pillar ligands, reactions. Also, their easy recyclability and reusability
H2dhbdc, at pH 13. The remaining ultrathin (2 nm) advantages further increase their potential as heterogeneous
nanosheets of the metal-organic layers, [Co 6 O- catalysts compared to homogeneous catalysts. A vast range of
(dhbdc)2(EtOH)4]2+, shown in Figure 216 after doping with organic reactions have been catalyzed by MOFs, which have
Fe(II), act as an efficient catalyst for OER with overpotential as been deeply covered and critically analyzed in several reviews
low as 211 mV at 10 mA cm−2 and TOF as high as 30 s−1 at reported until date.1485−1489 Now, the current research is also
overpotential of 300 mV.1462 Similarly, another 3D MOF has progressing with the development of 2D-based MOFs as
been converted into ultrathin nanosheets and tested for catalysts due to their sheet-like structure, which enables more
surface accessibility with active sites toward substrates by
overcoming the diffusion issue faced in 3D MOFs.1445,1490
Additionally, the coordinatively unsaturated metal centers and
defects present in 2D MOFs also make these more efficient
catalysts compared to 3D MOFs. In this section, we will focus
only on the 2D MOFs with selected examples for related
organic reactions.
The first example of MOF catalyst was revealed by Fujita et
al. in 1994, which is a square-grid 2D MOF, [Cd-
(bpy)2(NO3)2], and displayed the catalytic activity for the
Figure 216. 2D layer (a) and the 3D MOF with the pillar ligands (b) shape-selective cyanosilylation of aldehydes with trimethylsilyl
in (H3O)2[Co6O(dhbdc)2(H2dhbdc)2(EtOH)4]·2EtOH. Adapted cyanide (TMSCN) (Figure 217).106 Later study disclosed that
with permission from ref 1462. Copyright 2018 John Wiley & Sons. the presence of Lewis acidic Cd(II) centers promoted the
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towards cyclohexane substrate with 45% overall yield of

cyclohexanol and cyclohexanone products.1504 Similar reports
on oxidation of cyclohexane and cyclohexene to form
corresponding alcohol and ketones are also studied using
TBHP as oxidant.1505,1506 Interestingly, peroxidative allylic
oxidation of cyclohexene investigated by Li et al. using
[(Co(L)(H2O))2(H2O)] (H2L = 4-((1-carboxy-2-(1H-imida-
zol-4-yl)ethylaminomethyl)benzoic acid) as catalyst and
TBHP as oxidant yielded tert-butyl-2-cyclohexenyl-1-peroxide
Figure 217. 2D square grid [Cd(bpy)2](NO3)2 as a catalyst for as the major product (71.9% conversion in 6 h at 60 °C), along
cyanosilylation reaction. Reproduced with permission from ref 1486. with 2-cyclohexen-1-one and cyclohexene oxide as by-
Copyright 2019 Elsevier. products.1507 Another study based on aerobic oxidation of 4-
methoxybenzyl alcohol to 4-methoxybenzyl aldehyde using sql
cyanosilylation of imines with selectivity.1491 Another example and hcb net-based 2D Cu(II) MOFs has been also found.1508
is [Sc2(pydc)3(H2O)4]·5H2O, which with 10 mol % showed Oxidative coupling reactions are yet another class in this
99% conversion for p-nitrobenzaldehyde substrate in acetoni- context to be discussed. Konar and co-workers demonstrated
trile solvent within 1.5 h.1492 This showed higher activity that [Cu(tdc)(bpee)]·2H2O·MeOH (H2tdc = 2,5 thiophene-
compared to 1D and 3D frameworks reported therein. Monge dicarboxylic acid), a 2D pillared-bilayer MOF with 4-
and co-workers investigated the solvent-free cyanosilylation connected sq1 net exhibits good catalytic activity for Glaser
reaction carried out by [Ln(3,5-DSB)(phen)] (Ln = La, Pr, type homo-coupling reactions (Figure 218). This involves C−
Nd; 3,5-DSB = 3,5-disulfobenzoate), of which Nd-MOF (with
kgd topology) displayed slightly higher activity compared to
others. 1493 Their study on In-based 2D MOFs also
demonstrated solvent-free cyanosilylation catalysis.1494 Some
other reported 2D MOFs used as a heterogeneous catalyst in
cyanosilylation of aldehydes and ketones are also
noted.1495−1498
Recently, Paul et al. reported cyanosilylation of imines in
DCM solvent catalyzed by [Cd(L)(H2O)]·H2O and [Cd(L)]
(L = 5-(3,5-dimethyl-1H-pyrazol-1-yl) 1,3-benzenedicarbox-
ylate) 2D frameworks owing to Lewis acidic metal sites.1499
For N-benzylideneaniline substrate, 81% and 70% yield were
obtained in 4 h at room temperature, respectively.
Monge et al. demonstrated acetalization of benzaldehydes
with trimethyl orthoformate (TMOF) by four different 2D
MOFs, namely, [In(1,4-bdc)1.5(2,2′-bpy)] with inclined
polycatenated hcb layers, [In2(OH)2(1,4-bdc)2(phen)2] with Figure 218. (top) Possible mechanism for the Glaser oxidative
interdigitated sql net, [In(btc)(H2O)(2,2′-bpy)] with inter- coupling reaction. (bottom) View of 2D pillared-bilayer framework
digitated hcb net, and [In(btc)(H2O)(phen)] with interdigi- along the bc-plane. Adapted with permission from ref 1509. Copyright
tated fes net using Lewis acidic In(III) sites.1500 Highest 2014 Royal Society of Chemistry.
conversion of 76% has been achieved in the presence of
[In(btc)(H2O)(phen)]. C coupling of alkynes with in situ reduction of Cu(II) to
A 2D MOF [Co(Hoba)2·2H2O] (H2 oba = 4,4′-oxybis- Cu(I), which again at the end of reaction gets re-oxidized to its
(benzoic acid)) with (4,4) net topology reported by Li and co- original form in the presence of O2/air.1509 Other related
workers displayed solvent-free olefin epoxidation catalysis reactions are multicomponent coupling of an aldehyde, an
using tert-butyl hydroperoxide (TBHP) as oxidant, with very amine, and an alkyne to afford propargylamines and alkyne
high percentage conversion (96%) and selectivity (96%) hydration to ketones are also noted with moderate yield using
towards styrene substrate at 75 °C in 6 h.1501 Similar reports 2D MOFs.1510
are also found for hxl net based 2D MOFs, [Co3(1,4- Cycloaddition of CO2 with epoxides to produce industrially
bdc)3(DMF)2(H2O)2] and [Mn3(1,4-bdc)3(DMF)4] with valuable product cyclic carbonates is also investigated (Scheme
same percentage conversion but with less selectivity (45% 3). Park et al. analyzed different dimensional In-MOFs from
and 58%, respectively) in 1,2-dichloroethane (1,2-DCE) 1D to 3D, of which 2D MOFs, [In(1,4-bdc)1.5(2,2′-bpy)],
solvent at 75 °C in 7 or 9 h.1502,1503 [In(H2O)(btc)]·(H2O)·0.25bpy, [In(H2O)(btc)(phen)] and
Some other oxidation reactions based on free radical [In2(OH)2(1,4-bdc)2(phen)2], with 0.35 mol % and 0.35 mol
mechanism are also reported to be catalysed by 2D MOFs. % tert-butylammonium bromide (TBAB) co-catalyst, showed
Kirillov et al. investigated three 2D MOFs, [{Cu2(μ2-
dmea)2(H2O)}2(μ4-pma)]·4H2O, [{Cu2(μ2-Hedea)2}2(μ4- Scheme 3. Cycloaddition of CO2 to Propylene Oxide to
pma)]·4H2O, and [{Cu(bea)(Hbea)}4(μ4-pma)]·2H2O (H4 Form Cyclic Propylene Carbonate
pma = pyromellitic acid; Hdmea = [N,N-dimethylethanol-
amine; H 2 edea = N-ethyldiethanolamine; Hbea = N-
benzylethanolamine), with sql net for peroxidative cyclohexane
oxidation in the presence of acidic medium (H2O2 as oxidant,
Triflic acid/MeCN/H2O) and exhibited effective activity
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low to moderate catalytic performance (30−80% conversion) alkylation of indole with β-nitrostyrenes under mild reaction
toward propylene oxide conversion at 50 °C and 1.2 MPa CO2 conditions (3 mol %; 12 h and 35 °C) using [Zn2(2-
pressure in 12 h compared to reported 1D and 3D BQBG)(1,4-bdc)2]·10H2O (2-BQBG = 2,2′-(butane-1,4-
structures.1511 Although the highest conversion was achieved diylbis((quinolin-2-ylmethyl)-azanediyl))diacetamide). 1521
by 1D framework, [In2 (dpa)3 (phen) 2]·H2O (H2dpa = Other reports on Knoevenagel condensation reactions are also
diphenic acid) (91% conversion), due to more availability of noted.1198,1522 On the other hand, a secondary amide-
unsaturated Lewis metal sites, all frameworks exhibited >99% functionalized 2D MOFs, [Zn 2 (L)(H 2 O) 4 ]·4H 2 O and
selectivity. Another report by Wang and co-workers inves- [Cd 3 (HL) 2 (DMF) 4 ]·4DMF (L = 5,5′-(pyridine-2,6-
tigated a series of 2D In-MOFs, namely, (Me2NH2)[In(SBA)2] dicarbonyl)bis(azanediyl)}diisophthalate). showed catalytic
(fes net), (Me2NH2)[In(SBA)(1,4-bdc)] and (Me2NH2)[In- activity towards one-pot cascade deacetalization−Knoevenagel
(SBA)(NH 2 -bdc)] (1D to 2D interpenetrated) and condensation reactions under mild conditions.1523 Konar et al.
(NH4)3[In3Cl2(bpdc)5] (pentagonal layer) (H2SBA = 4,4′- investigated the catalysis of aldol condensation of aldehydes
sulfonyldibenzoic acid) as catalysts for this reaction.353 The using [Mg2(HL)2(H2O)4]·H2O (H3L = pyrazole-3,5-dicarbox-
order of catalytic activity is (NH4)3[In3Cl2(bpdc)5] > ylate) in the presence of excess ketone at 5−10 °C in 3:1
(Me2NH2)[In(SBA)(NH2-bdc)] > (Me2NH2)[In(SBA)(1,4- THF−water solvent mixture. The best result was obtained for
bdc)] > (Me2NH2)[In(SBA)2]. Of these, the best catalytic p-nitrobenzaldehyde and acetone with 82% isolated yield in 6
activity was exhibited by (NH4)3[In3Cl2(bpdc)5] (0.1 mol %) h.1524
for propylene oxide substrate with 98% conversion (TON = C−C bond formation using Baylis−Hillman and Henry
980) in the presence of TBAB co-catalyst at 80 °C and reactions has been demonstrated in 2D MOFs,
anticipated due to the presence of unsaturated octa- and hepta- [Zn 3 (L) 3 (urotropine) 2 ]·2DMF·3H 2 O and [Zn 8 (L) 6 (μ 3 -
coordinated Lewis acidic In(III) centers. A sql net 2D MOF OH)4(H2O)6]·(DMF)·(H2O)2.5 (H2L = 5-benzylamino)-
[Cu{C6H4(COO−)2}2]·2C9H14N3(C9H14N3 = 1-(2-pyridyl)- isophthalic acid).1240,1249 2D MOF, [Cu2(BPTC)(Im)4(H2O)-
piperazine; C6H4(COO−)2 = o-phthalate) showed 80% yield (DMF)] (H4BPTC = biphenyl-3,3′,4,4′-tetracarboxylic acid;
(TON = 1600) for 2-(hydroxymethyl)oxirane product.1512 Im = imidazole), catalyzed hydroxylation of phenol with H2O2
Diniz and co-workers reported the catalytic performance of at 40°C for 4 h with selectivity towards diphenols.1525 Alkane
[Nd(5-sis)(H2O)4] (5-sis = 5-sulfoisophthalic acid) and its (linear/cyclic) hydrocarboxylation by [Cu2Mg2(μ-Htea)2(μ6-
activated form towards glycerol carbonate formation from pma)(H2O)6]·6H2O (H3tea = triethanolamine; H4pma =
glycerol and urea with 76%/74% conversion and 74%/81% pyromellitic acid) is also reported.1526 [Cu2(tart)2(H2O)2]·
selectivity, respectively.1513 A few cyclization reactions are also 4H2O (tart = D-tartrate) is reported to catalyze allylation of
noted in heterogeneous catalysis by 2D MOFs. For example, aldehydes in the presence of DCM:H2O mixture.1527 Hydro-
formation of 2-(pyridin-4-yl)-1,4,5,6-tetrahydropyrimidine by boration of ketones with pinacolborane by [Fe(L)2Cl2] (L =
the reaction of 4-cyanopyridine with 1,3-diaminopropane is 4′-(4-diphenylaminophenyl)-4,2′;6′,4″-terpyridine)1528 and
catalyzed by isostructural 2D MOFs, [M2(L)(py)6]·H2O (M = transesterification of carboxylate esters using [Zn2(μ-L-
Cd, Co, Ni, Cu; H4L = 5,5′-(1H-2,3,5-triazole-1,4-diyl)- 1κO:2κO′)2(bpy)2(H2O)]·2DMF·5H2O (H2L = 5-propiona-
diisophthalic acid) in accordance to the Lewis acidity strength midoisophthalic acid) are also investigated.1529 Also, 2D
of metal centers.1514 Another reaction involving of synthesis of Cu(II) MOF, [Cu(imidazole)2] catalyzed N-arylation of
3,6-bis(pyridin-4-yl)-1,2,4,5-tetrazine from 4-cyanopyridine imidazole with phenyl boronic acid (86% yield) in MeOH
and hydrazine hydrate using a Ni-based 2D MOF is also with 5 mol % catalyst at room temperature.1530
studied.1515 While ring opening of styrene oxides with amines Moreover, 2D MOF-based or derived nanostructures are
and methanol using [Cd(tpim)(1,5-nds)] (1,5-nds = 1,5- also competing with good catalytic activity in different
naphthalenedisulfonate; tpim = 2,4,5-tri(4-pyridyl)-imidazole) reactions. La2O2CO3 and La2O3/SrCO3/La2O2CO3 obtained
and [Gd2(H3nmp)2]·xH2O (H6nmp = nitrilo- by the thermal decomposition of (NH 4 ) 2 [La 2 (1,3-
(trimethylphosphonic)acid), respectively, are also stud- pdta)2(H2O)4]·8H2O (1,3-H4pdta = 1,3-propanediaminetetra-
ied.1516,1517 acetic acid) and [La 2 (1,3-pdta) 2 (H 2 O) 4 ]·[Sr 2 (H 2 O) 6 ]·
Condensation reactions including Knoevenagel and aldol [La2(1,3-pdta)2(H2O)2]·18H2O at 600 °C, respectively,
condensation have been catalysed by 2D MOFs as well. A kgd exhibited good catalytic activity toward oxidative coupling of
net based 2D MOF, [Nd 2 (TATMA) 2 ]·4DMF·4H 2 O methane.1531 These showed 23% and 29.7% conversion with
(H3TATMA = 4,4,4″-s-triazine-1,3,5-triyltri-m-aminoben- C2 selectivity of 45.8 and 51.7% at 700 °C, respectively.
zoate), served as a heterogeneous base catalyst due to the Similarly, CuO nanoparticles obtained from
presence amine groups for Knoevenagel condensation reaction [Cu4(CN)5(C5H5N)4] catalyzed cross-coupling C−N, C−O,
between benzaldehyde and malononitrile in toluene afforded and C−S reactions with aryl halides.1532
95% yield at 80 °C in 3 h.1518 Mandal and co-workers reported 2D MOF nanosheets, [Hf6(μ3-O)4(μ3-OH)4(HCO2)6-
a primary amide-functionalized hcb net, [Cd2(2-bpbg)- (TPY)2] (TPY = 4′-(4-carboxyphenyl)-[2,2′:6′,2″-terpyri-
(fum)2(H2O)2]·8.5H2O (2-bpbg = N,N′-bis(2-pyridylmeth- dine]-5,5′′-dicarboxylate), with kgd net upon metalation
yl)-1,4-diaminobutane-N,N′-diacetamide; fum = fumarate), with CoCl2 and FeBr2, respectively, and activation with
displayed effective catalysis with 2 mol % toward Knoevenagel NaEt3BH generated Co(THF)2·TPY-MOF and Fe(THF)2·
condensation reaction for benzaldehyde substrate with 100% TPY-MOF, which act as highly efficient catalysts for C−H
conversion in 1 h owing to both Lewis acidic unsaturated activation reactions: benzylic C−H borylation of methylarenes
Cd(II) centers and Brønsted basic primary amide moieties.1519 and intramolecular Csp3−H amination of alkyl azides to afford
Its Zn(II) analogue (3 mol %) showed Michael addition of pyrrolidines and piperidines, respectively (Figure 219).1533
malononitrile to 2-enoylpyridines in 1 h with 99% With 1 mol % of Co(THF)2·TPY-MOF loading, m-xylene
conversion.1520 Later they reported hydrogen-bond donating borylation with B2pin2 afforded 95% yield for aryl and benzyl
(HBD) heterogeneous catalysis for the Friedel−Crafts borylated products with a higher selectivity for benzylic
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100% yield toward anti-Markovnikov product with TON =

>5000 in 48 h, which was superior compared to 3D interlocked
and stacked structures prepared as control catalysts.
Zhao and co-workers featured fast precipitation of kinetically
controlled product: Zr/Hf MOF nanosheets built of
Zr6O4(OH)4 or Hf6O4(OH)4 clusters and 1,3,5-benzenetri-
benzoate (BTB3−) with a thickness of 10−20 nm,1535 while
conventional solvothermal conditions (DMF/acetic acid, 120
°C for 24 h) yielded thermodynamically controlled product-
3D interpenetrated framework. The obtained 2D MOF
nanosheets have been used to catalyze the oxidation of anisole
(PhSCH 3 ) to generate the corresponding sulfoxides
(PhSOCH3) and sulfones (PhSO2CH3) using 30% H2O2
oxidant in DCM at 298 K. With 1.5 mol % catalyst, >99%
conversion took place with 100% selectivity for sulfone
product, which is better than corresponding 3D MOFs.
In addition to these, 2D MOF-based nanocomposite
catalysts are a major field of inspiration and attraction
nowadays for many material scientists. Maji et al. investigated
Cu2O nanoparticles embedded inside the desolvated honey-
comb 2D MOF, [Zn(Himdc)(bpy)0.5]·DMF (Himdc = 4,5-
imidazoledicarboxylate), to catalyze the Huisgen 1,3-dipolar
cycloaddition reaction of terminal alkynes and aliphatic/
aromatic azides (known as Click reaction) to produce 1,2,3-
triazoles (Figure 220).1536 This catalyst with 0.5 mol % is
capable of completing the reaction with 98% yield in 7 h at 50
°C for different types of alkynes and azides substituted with
electron donating/withdrawing groups. The same group also
Figure 219. 2D M·TPY-MOFs, constructed from Hf6 SBUs and TPY previously demonstrated Pd(0) nanoparticles inside this MOF
and then metalated with Co and Fe, were used for benzylic C−H for a multicomponent coupling reaction to form propargyl-
borylation and intramolecular sp3 C−H amination reactions, amine derivatives.1537 Additionally, Ru nanoparticles inte-
respectively. Reproduced with permission from ref 1533. Copyright
grated Zr-(1,4-bdc) MOF (UiO-66) nanosheet composites
2018 Royal Society of Chemistry.
formed by biosurfactant mediated process served as a catalyst
in the hydrogenation of levulinic acid (LA) to γ-valerolactone
borylation (4.6:1) at 100 °C in 3 days. On the other hand, 2 (GVL) with higher activity compared to its pristine or other
mol % Fe(THF)2·TPY-MOF loading, intramolecular Csp3−H commercial Ru/C and reported Ru/ZrO2 catalysts.1538
amination of 1-azido-4-phenylbutane in the presence of di-tert- Similarly, Zeng et al. demonstrated binary ultrafine alloy
butyl dicarbonate (Boc2O) yielded 89% Boc-protected α- NiPd nanoparticles supported onto 2D MgAl layered double
phenyl pyrrolidine at 90 °C, while a similar reaction with 7- hydroxides and/or oxides (LDH/LDO) formed from liquid-
azidohept-1-ene yielded 34% of Boc-2-vinylpiperidine product. phase reduction or thermal autoreduction of intercalated
Similarly, Lin et al. investigated [Hf6O4(OH)4(HCO2)6- cyanometalate ([M A (CN) n ] 2−/3− (n = 4 or 6)) and
(BTB)2] (BTB = benzene-1,3,5-tribenzoate) nanosheets (kgd chlorometalate [MBCl4]2− to catalyze carbon−carbon cross-
net), which upon doping with TPY, metalation with FeBr2, and coupling reactions such as Suzuki−Miyaura, Heck, and
activation by NaEt3BH produced the final 2D MOF nano- Sonogashira reactions.1539 Suzuki−Miyaura reaction between
catalyst (Fe-TPY-MOF) for hydrosilylation of olefins.1534 At iodobenzene and phenylboronic acid afforded 97% yield in 30
0.02 mol % catalyst loading for styrene substrate afforded min, Heck coupling between iodobenzene and methyl acrylate

Figure 220. Schematic diagram showing the stabilization of Cu2O nanoparticles in desolvated 2D MOF, [Zn(Himdc)(bpy)0.5]·DMF, and the
catalytic azide−alkyne cycloaddition reaction. Reproduced with permission from ref 1536. Copyright 2015 Royal Society of Chemistry.

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Figure 221. (a) Modifying the SBUs of [Hf6O4(OH)4(HCO2)6(TPY)2] with gluconic acid (GA) and Fe2+ for the selective oxidation of
tetrahydrofuran. Reproduced with permission from ref 1543. Copyright 2017 John Wiley & Sons. (b) Synthesis of Hf-BPY and Hf-IrBPY 2D MOF
nanosheets for (c) photopolymerization of methyl methacrylate. Adapted with permission from ref 1545. Copyright 2018 American Chemical
Society.

afforded 100% yield in 1 h and Sonogashira reaction between (ppy = bis(2-phenylpyridine)) generated [Hf6(μ3-O)4(μ3-
iodobenzene and phenylacetylene afforded 95% yield in 1 h. OH)4(HCO2)6(BPY)2{Ir(ppy)2Cl}1.56] (Hf-IrBPY) (Figure
Incorporation of ultrasmall Au nanoparticles (0.94−1.58 nm) 221b,c), which is used as a catalyst for photopolymerization
inside the 2D nanosheets of [Ni2(5,4-PMIA)2(TPOM)0.5]· of methyl methacrylate with 78% conversion (using ethyl α-
xSolvent (5,4-PMIA = 5-(4-pyridyl)-methoxyl isophthalic bromophenylacetate, EBP as co-initiator) and 65% conversion
acid) formed via surfactant-assisted method has been utilized (in absence of EBP) under 410 nm LED light.1545 Photo-
as a catalyst showing good size selective activity for 4- reduction of CO2 to CO has been displayed by Zn-TCPP 2D
nitrophenol (4-NP; size: 2.4 × 6.1 Å2) reduction to 4- nanosheets as a photosensitizer in the presence of co-catalysts,
aminophenol using NaBH4 compared to Mordant Green 17 [Co2(OH)L](ClO4)3 (L = N[(CH2)2NHCH2(m-C6H4)-
(MG 17; size: 7.2 × 14.0 Å2).1540 This nanocomposite catalyst CH2NH(CH2)]3N) or ZIF-67 (ZIF = zeolite imidazolate
with 0.94 nm Au nanoparticles displayed the complete framework) as co-catalyst with 91% selectivity for CO
reduction of 4-NP within 6 min monitored by UV−vis (TONCO = 117.8 and TONH2 = 11.6).1546 Photocatalytic
spectroscopy (bright yellow to colorless) with pseudo-first- oxidation of 1,5-dihydroxynaphthalene to juglone has been
order rate constant of 0.404 min−1. achieved by ultrathin Zr-NiTCPP MOF nanosheets formed by
Other than these reactions, oxidative condensation of modulator-mediated solvothermal process via pseudoassembly-
furfural with n-propanol to produce 3-(furan-2-yl-)-2-methyl- disassembly strategy.1547
acrylaldehyde in the presence of molecular O2 catalyzed by Additionally, photocatalytic degradation of organic pollu-
carbon@2D Co-MOF ([Co(tia)(H2O)2)]; tia = 5-(1H-1,2,3- tants such as dyes is also accounted by 2D MOFs bearing
triazol-1-yl)isophthalate)) nanocomposite and alkene hydro- narrow band gaps for water purification. The mechanism of
genation catalyzed by Pd nanoparticle supported onto [Zn(2- this reaction is mediated by the excitation of electrons by
MeIm)2] (MeIm = methylimidazolate) 2D layered framework photoirradiation from valence band to conduction band which
are also reported.1541,1542 simultaneously form holes (h+), and these two species combine
5.11.1. Photocatalysis. Lin and co-workers and others with water and oxygen molecules to generate hydroxyl (•OH)
have investigated a few modulator-assisted 2D MOF nano- and superoxide (•O2−) radicals, respectively, the oxidizers for
sheets as photocatalysts for various types of reactions. In one decomposing the dye molecules into CO2, H2O etc. As a
report, they demonstrated the tuning of hydrophobicity/ representative example, a 2D to 3D parallelly polycatenated
hydrophilicity around the active sites in MOF [(Ti3O)(iPrO)8]1.5[L]3[Cu4I4] based on tetrahedral
[Hf6O4(OH)4(HCO2)6(TPY)2] with Fe2+ as well as Fe2+/ Cu4I4 clusters with 1.70 eV band gap displayed better
gluconic acid (GA) for the selective photocatalytic oxidation of degradation of methylene blue (MB), rhodamine B (RhB),
tetrahydrofuran (THF) to produce butyrolactone (BTL) and and methyl orange (MO) dyes with efficiencies of 100% in 12
2-hydroxytetrahydrofuran (2-OH-THF) using a blue LED min, 98% in 20 min, and 98% in 28 min, respectively (Figure
lamp (Figure 221a).1543 It is observed that in the presence of 222) compared to the other 2D MOFs reported therein.1548
gluconic acid, BTL with 100% selectivity (TON = (5.3 ± 0.3) Radical scavengers such as isopropyl alcohol for •OH,
× 102), whereas without it, only 57.3% selectivity (TON = (8.2 benzoquinone for O2•− and ammonium oxalate/EDTA-2Na
± 0.3) × 102) were obtained. Using photoactive [Zr6(μ3- for h+ were also introduced to prove the involvement of
O) 4 (μ 3 -OH) 4 (HCO 2 ) 6 (BPY) 2 {Ru(2,2′-bpy) 2 Cl 2 } 1.42 ](Zr- reactive radical species reflected through decrement in
RuBPY) (H3BPY = 4′,6′-bis(4-benzoic acid)-(2,2′-bipyridine)- photodegradation efficiency.1213,1549−1552 Similarly, a few
5-carboxylic acid) synthesized via post-synthetic treatment other 2D MOFs for dye degradation are also reported.1553−1576
with Ru(bpy)2Cl2 showed photocatalytic activity toward [2 +
2] cycloadditions of bis(enones), crossed cycloaddition of 5.12. Miscellaneous Properties and Applications
enones and reductive cyclization of bis(enones).1544 Similarly, The thermoelectric properties of crystalline 2D MOFs,
pos t -s ynt h et ic all y m e ta la tio n of H f 6 + a n al og u e , [M3(HITP)2], (M = Ni, Pd or Pt), have been studied using
[Hf6O4(OH)4(HCO2)6(BPY)2] (Hf-BPY) with [Ir2(ppy)4Cl2] ab initio transport models, classical molecular dynamics
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Figure 222. (a) 2D to 3D parallelly polycatenated structure of

[(Ti3O)(iPrO)8]1.5[L]3[Cu4I4]. (b) Time-dependent UV-vis spectra
of three dyes (MB, RhB and MO) and color change photograph
images of the dye solutions over photocatalyst MOF. Adapted with
permission from ref 1548. Copyright 2018 John Wiley & Sons.

simulations, and the Landauer formalism. It is predicted that

these materials to have high thermoelectric efficiency due to
the large Seebeck coefficient and low thermal conductivity.1577
Another 2D MOF compound [Pb(Tab)2(bpy)](PF6)2 (Tab =
4-(trimethylammonio)benzenethiolate) shows very low dielec-
tric constant (low-κ) and low dielectric loss in the high electric Figure 223. (a) Crystal structure of[Co2(Glu)2(μ-bpe)2]·(H2O)0.5.
field frequency range. At 30 °C, the dielectric permittivity, ε is (b) Percentage of inhibition rate of Candida albicans by the Co(II)
in the range 8.39−2.53 with the frequency increasing from 102 MOF. Reproduced with permission from ref 1582. Copyright 2017
to 106 Hz which is lower than SiO2.1578 American Chemical Society.
Thermal expansion studies in the single crystals of
[Mn(salen)]2[Mn(N)(CN)4(G)], (salen = N,N′-ethylenebis-
(salicylideneaminato), G = MeOH and MeCN) revealed that Under this scenario, the fabrication of advanced 2D materials,
the combination of both positive and negative thermal such as MOFs, covalent organic frameworks (COFs), and
expansion in the temperature range 380−440 K resulted in graphene oxides (GOs), has been considerably investigated to
zero in-plane thermal expansion.1579 Another 2D MOF afford newly developed composites exhibiting varied interest-
[Ag(tcm)] (tcm = tricyano-methanide anion) with twofold ing features and applications.9,13,1583−1588 Of these, our main
interpenetrated hexagonal (6,3) net occupied in the ac plane focus is to provide an overview on 2D MOF-based composite
shows coefficients of thermal expansion of −48(3), +200(2), materials that are mostly obtained from their nanosheet forms
and −54(4) M K−1 along a, b, and c axes, respectively.1580 The via immobilization with other hybrid structures such as
negative thermal expansion in the 2D sheet of Zn(CN)2 graphene oxides, graphitic carbon, and metal surfaces,
(−16.9 × 10−6 K−1) and Cd(CN)2 (−20.4 × 10−6 K−1) M nanoparticles, organic polymers, etc. Their vast range of
K−1 is the largest compared to Ni(CN)2 (−6.5 × 10−6 applications including electrocatalysis, supercapacitors, ther-
K−1).1581 Variable-pressure measurements in the pressure mochromic properties, sensing, and gas separation will also be
range of 0 < p < 0.615 GPa provided additional insights for discussed in each of the respective cases provided in the
this process. subsections.
Antifungal activity has been investigated in a 2D Co(II) 6.1. Nanocomposites of 2D MOFs with Carbon Surfaces
MOF, [Co2(Glu)2(μ-bpe)2]·(H2O)0.5, made up of glutarate 6.1.1. With Graphene. Graphene and MOF composites
(Glu) and bipyridyl ligand, bpe with high inhibition rate using a 2D pillared-bilayer MOF such as [Cd4(azpy)2(pydc)4-
toward fungal pathogens, and Candida albicans (99.98%) (H2O)2]·9H2O, can be made with benzoic acid functionalized
compared to Aspergillus niger (62%) under the maximum graphene or graphene oxide via growth of MOF nanosheets on
concentration of 2 mg mL −1 (Figure 223). 1582 The graphene surfaces.1589 The reported composites exhibited a
mechanistic pathway involves the generation of reactive species two-step type-I CO2 uptake with a large hysteresis unlike a
NO and H2O2 which are vital for the inhibition process. single step as observed from the pristine MOF (Figure 224).
Such an example illustrates the possibility of tuning properties
6. 2D MOF COMPOSITES AND THEIR APPLICATIONS when 2D MOFs are made into composites with other 2D
In recent years, the advancement in the state-of-the-art materials.
development of hybrid composite materials has been widely 2D Ni(II) MOF based on squaric acid and polyvinylpyrro-
achieved owing to their broad range of applications in different lidone (PVP) obtained by polymer-templated approach has
fields. These applications are found to be boosted in been fabricated into Ni7S6/graphene nanosheet (GNS)
comparison to the precursor materials utilized for their heterobilayers using in situ sulfidation in the presence of
formation. During earlier times, the chemists focused on thiourea (Figure 225).1590 This composite with synergistic
organic polymers as precursors to produce composite materials effect exhibits excellent electrochemical performance compared
which mainly have dominance over the membrane field.1583 to NiS/graphene and metal disulfide-based composite electro-
However, these polymers lack chemical and thermal stability des. Another example is based on cobalt oxide (Co3O4) 2D
upon exposure to harsh reaction conditions, which spurred the nano-assemblies derived from 2D Co(II)-Hppd MOF (Hppd
need for a superior form of composite hybrids. Other than = N,N,N′,N′,N″,N″-hexa(4-pyridyl)-1,3,5-phenylenediamine)
these, zero dimensional nanomaterials-based composites with as a precursor, which is integrated into graphene (G) to
metallic surfaces are also developed but suffers limitations like form Co3O4/G nanocomposite and utilized for lithium battery
long-term stability, structural robustness, and biocompatibility. applications.1434
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Figure 226. (a) Chemical structure tecton (P). (b) Zoom-in STM
current image of a monolayer of free tecton P with the proposed
molecular packing motif. Adapted with permission from ref 1591.
Copyright 2014 Royal Society of Chemistry.

Figure 224. Schematic representation of intercalation of 2D Cd-PBM

between functionalized graphene sheets. Adapted with permission
from ref 1589. Copyright 2014 Royal Society of Chemistry.

Figure 227. (a) Schematic diagram for the preparation of 2D CoSNC

nanocomposites. (b) XRD pattern of 2D CoSNC nanocomposites.
(c) AFM image of 2D CoSNC nanocomposites. Inset: Statistical
analysis of the thickness of 75 2D CoSNC nanocomposites measured
in AFM images. (d) TEM image of a typical 2D CoSNC
nanocomposite. Top inset: TEM image taken from the white square
Figure 225. (a) Schematic diagram showing the formation of 2D in the main panel. Bottom inset: SAED pattern of 2D CoSNC
Ni(II) MOF layers from 3D MOF. On the basis of experimental nanocomposites. (e) HRTEM image of 2D CoSNC nanocomposites.
evidence, PVP acts as a structure-directing agent. (b) In situ synthesis (f) Annual dark-field TEM image of 2D CoSNC nanocomposites and
of heterobilayer composite of 2D graphene with nickel sulfide from the corresponding EDX elemental mapping images of elements C, Co,
Ni(II) MOF sheets using thiourea via solvothermal conditions. S, and N. Adapted with permission from ref 1439. Copyright 2016
Reproduced with permission from ref 1590. Copyright 2019 John & American Chemical Society.
Wiley Sons.

S) and bpy (source of N) (Figure 228).1592 In comparison to

6.1.2. With Graphite. Similarly, a 2D MOF showing the pristine Co-Ni MOF and CoSNC, this composite displayed
nanopatterns on graphite surface via self-assembly of the high supercapacitor performance with specific capacitance of
porphyrin-based acentric tecton (5,15-dipentyl-10-(4-yl-pyr-
idine)-20-(4-yl-ethynylpyridin)porphyrin (P) and metallatec-
ton cobalt chloride can be generated.1591 The formation of the
2D MOF at the solid−liquid interface was monitored by
scanning tunneling microscopy (STM) imaging as well (Figure
226).
Zhang et al. demonstrated the preparation of a 2D CoS1.097/
nitrogen-doped carbon nanocomposite (CoSNC) based on a
2D porphyrin paddlewheel Co-MOF (PPF-3) nanosheets and
obtained by a combinatorial method of sulfidation and
carbonization of MOF nanosheets (Figure 227).1439 CoSNC
acts as a supercapacitor electrode with high rate capacitance
value of 360.1 F g−1 at a current density of 1.5 A g−1 and
prolonged cycling activity.
On the basis of a similar protocol, Zhao and co-workers Figure 228. Schematic diagram for the fabrication of the 2D CoNi@
reported a 2D CoNi alloy nanoparticles@S,N-doped porous SNC composites. (a) Constitution unit, (b) Co-MOFs, (c) Co/Ni
carbon (CoNi@SNC) composite via pyrolysis of Co−Ni 2D MOFs, (d) CoNi@SNC. Reproduced with permission from ref 1592.
nanosheets containing thiophene-2,5-dicarboxylate (source of Copyright 2017 Royal Society of Chemistry.

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1970, 1897, and 1730 F g−1 at 1, 2, and 5 A g−1, respectively, reddish-brown crystals without the intercalation of C60, which
and long shelf lives. Similar approach was also observed to acts as a steric template to direct the formation of the 2D
form Co3O4@porous carbon composites from ZIF-67 2D structure (Figure 230). When C70 was used instead, a 3D
nanosheets with supercapacitor activity.1593 Similarly, a 2D intercalated structure CuAcO-CuTPyP·C70@m-DCB·CHCl3
Co(II) MOF based on 2-methylimidazole grown on carbon was obtained formed by 2D sheets with intercalated C70
cloth (CC) surface has been used as a precursor to oxidize into fullerene. This also exhibits interpenetration with another set
Co3O4 nanosheets (CC@Co3O4) and also transformed to N- of similar 2D sheets. Both structures were confirmed by XRD
doped porous carbon nanosheets (CC@NC) via thermal technique. These porous materials after activation are believed
treatment.1594 These two were assembled as cathode and to exhibit selective sorption as well as catalytic properties.
anode, respectively, using poly(vinyl alcohol) (PVA)−KOH 6.2. Nanocomposites of 2D MOFs and Hybrid Materials
gel-electrolyte to generate a flexible asymmetric supercapacitor.
Utilizing nickel-cyano MOF nanosheets prepared at 400 °C Apart from the above-mentioned composite forms, there are
in Ar/H2 mixed gas followed by doping with Fe atom, Fe@ some other composites in which 2D MOFs have been
Ni3C nanodots in N-doped carbon nanosheets were formed by hybridized with other functional materials to develop hybrid
Yan et al.1595 This composite exhibits excellent electrocatalyst nanosheets and thin films. Some of these examples are
activity at a low overpotential (292 and 275 mV) and a small presented below.
Tafel slope (41.3 and 62 mV dec−1) for HER and OER in basic 6.2.1. With Nanoparticles. Here, the composite hybrids
solution, respectively. Another example on graphitic carbon− prepared using metal, metal oxide, and metal sulfide nano-
metal phosphide nanocomposite is Co-P@N-doped carbon particles (NPs) united with 2D MOFs are discussed. Some of
(Co-P@NC) derived from a previously reported 2D MOF the nanocomposite examples of this category are also provided
PPF-3 nanosheet1439 has been described by Du et al. (Figure in section 5.11.1536−1542 An enzyme mimic nanosheet
229).1596 This also shows good electrocatalytic activities for composite has been reported by Zhang and co-workers
produced by the integration of 2D metalloporphyrin Cu-
TCPP(M) (M = Fe, Co) nanosheets into Au NPs (Figure
231a).1598 This hybrid nanosheet possess both peroxidase-like
and glucose oxidase-like activities from 2D MOF nanosheets
and Au NPs, respectively. Hence, it acts as an enzyme-mimic
catalyst for cascade reactions and can also detect biomolecules
such as glucose (Figure 231b). 2D ZIF nanosheet membranes
coated with ZnO NPs via ammonia-assisted process is also
reported exhibiting potential H2/CO2 gas separation activ-
ity.867
Robust in situ synthetic approach of 2D M-TCPP nano-
sheets-metal sulfide NPs based composite was also introduced
(M = Cu, Cd, or Co) by Zhang’s laboratory.1599 Especially, a
composite consisting of Cu-TCPP nanosheet and copper
sulfide NPs can be obtained by sulfidation of the Cu-TCPP
nanosheets in ethanol. The reaction of copper from the 2D
MOF with thioacetamide in ethanol resulted in the formation
of CuS hybridized with the 2D MOF (Figure 232). The
composite when used as an active material for photo-
electrochemical cells, exhibited increased photocurrent re-
sponse compared to the pure Cu-TCPP nanosheet alone.
An effective and facile dual-step strategy based on alloying of
Figure 229. (top) Schematic illustration for the synthesis of Co-P@ bimetallic Fe3O4 and Au NPs with 2D Cu(Hbtc) MOF
NC. (bottom) SEM images of (a) PPF-3 nanosheets (inset shows nanosheets under ambient conditions to form hybrid nano-
enlarged nanosheets), (b) Co@NC-800, and (c) Co-P@NC-800. (d) material has been demonstrated by Quan et al.1600 Cu(Hbtc)-
TEM and (e) HRTEM images of Co-P@NC-800. (f) SAED patterns 1/Fe3O4-AuNPs nanosheet composite was applied for flexible
of Co-P@NC-800, showing diffraction spots of CoP and Co2P. DNA regulation with upgraded peroxidase-like catalytic
Adapted with permission from ref 1596. Copyright 2017 American activity compared to its precursor material and subsequently
Chemical Society. explored for colorimetric sensing of H2O2 and glucose (Figure
233). In addition, its performance as a label-free colorimetric
both HER and OER with a current density of 10 mA cm−2 at aptasensor toward SDM detection at 1.70 μg L−1 level was also
low overpotentials of 98 and 370 mV in acidic and basic media, accomplished. This study exemplified the role of 2D MOF
respectively. The previously mentioned protocols used paved a composites in environmental monitoring and biological
way for the implementation of 2D MOFs as template in diagnosis as a colorimetric assay.
generating potential water-splitting electrocatalysts. 6.2.2. With CdSe Quantum Dots and Au Nano-
6.1.3. With C60 and C70 Fullerenes. The synthesis of particles. The combination of both quantum dots and
square grid 2D porphyrin MOFs (P-MOFs) with fullerene C60 metal nanoparticles has also been assembled to produce 2D
and C70 has been reported by Tatsumi et al.1597 The composite MOF composites. Sreedhar and co-workers demonstrated a
MOF, CuAcO-CuTPyP@m-DCB, obtained by the layering simple post-synthesis surface modification method to develop
reaction of H2TPyP (5,10,15,20-tetra-4-pyridyl-21H,23H- composites of 2D La-btc nanosheets sensitized with surface
porphyrin), copper(II) acetate (CuAcO), and C60, afforded plasmon resonance (SPR) active Au nanoparticles (NPs) and
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Figure 230. (a) Construction of P-MOFs incorporating cavities in the presence of C60 and C70 fullerenes. (b) Crystal packing structure of CuAcO-
CuTPyP@m-DCB. (c) (left) Details of the noncovalent interactions between CuTPyP and C70 in CuAcO-CuTPyP·C70@m-DCB·CHCl3 and
(right) its interpenetrated structure (colored separately in sky blue and pink) showing the large void spaces, viewed from approximately down the c-
axis. For clarity, guest molecules were omitted. Adapted with permission from ref 1597. Copyright 2016 John Wiley & Sons.

Figure 231. Schematic illustration of (a) synthesis of Au NPs/Cu-

TCPP(M) hybrid nanosheets (M = Fe, Co) and (b) enzyme-mimetic
cascade reaction catalyzed by the composite MOF. Adapted with
permission from ref 1598. Copyright 2017 John Wiley & Sons. Figure 232. (a) Schematic diagram of preparation of CuS/Cu-TCPP
composite nanosheet. (b) Schematic illustration of the fabricated
photoelectrochemical cell. Inset: photograph of the Cu-TCPP
nanosheet film on FTO glass. (c) LSV curves of the pure Cu-
CdSe quantum dots (QDs).1601 This nanocomposite displayed
TCPP nanosheets and CuS/Cu-TCPP-n composite nanosheets under
enhancement in the light harvesting properties owing to illumination of chopped AM 1.5G. (d) Transient photocurrent
cooperative effect of both NPs and QDs present in it. Besides responses of the pure Cu-TCPP nanosheets and CuS/Cu-TCPP-n
demonstrating exceptional stability in photoelectrochemical composite nanosheets under illumination of chopped AM 1.5G at a
water splitting for a time span of 10 h, the composite also acted fixed bias potential of −0.6 V (vs Ag/AgCl). Adapted with permission
as a heterostructure anode to generate current density of ∼80 from ref 1599. Copyright 2016 John Wiley & Sons.
mA/cm2 at 0.8 V (vs Ag/AgCl). Moreover, the post-treatment
examination revealed the phase transformation of CdSe QDs
to CdS nanosheets occurred via leaching process that further nanosheets with Au nanoclusters to form 2D AuNCs@521-
strengthened the stability of the composite as well as amplified MOF composite nanosheets is also noted in the literature
photoelectrochemical water splitting response (Figure 234). (Figure 235).1602 Its features like high surface area, electro-
6.2.3. With Au Nanoclusters. One-pot self-assembly chemical response, and biocompatibility allowed its modifica-
method for the immobilization of a 2D Zr-MOF (521-MOF) tion into a highly sensitive aptasensor for detecting cocaine in
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6.2.4. With MXene Phase. Huang and co-workers

demonstrated an interesting methodology named “interdiffu-
sion reaction-assisted process” to form nanosheet composites.
This involves in situ amalgamation of 2D Co-(1,4-bdc)
framework and MXene phase of electrically conductive
Ti3C2Tx.1603 The ultimate hybrid material displays remarkable
electrocatalytic activity towards OER at a lower potential with
a current density of 10 mA cm−2 in 0.1 M alkaline solution
(Figure 236). It has been used for fabrication into a
rechargeable Zn-air battery device to power a red light-
emitting diode.
Figure 233. Schematic diagram of peroxidase-like activity and its 6.2.5. With Textiles. Conductive Ni-based 2D MOFs on
controllability regulated by DNA of Cu(Hbtc)-1/Fe3O4-AuNPs wearable electronic textiles (e-textiles) has been fabricated by
nanosheets. Reproduced with permission from ref 1600. Copyright Mirica and co-workers.1604 2D MOFs were synthesized by
2017 Royal Society of Chemistry. direct self-assembly of HHTP or HATP with nickel(II) salts,
while the integrated 2D MOFs into e-textiles were fabricated
by direct solution-phase self-assembly process. The resulting
composites termed as self-assembled frameworks on textiles
(SOFT) show enhanced functional utilities such as reliable
conductivity, improved porosity, flexibility, and cleaning
stability (Figure 237). Furthermore, these devices act as both
chemiresistive probes and sequesters for recognizing gaseous
analytes NO, H2S, and humidity at ppm level and filtering off
NO and H2S.
Parson and co-workers demonstrated the fabrication of
water-stable 2D M-TCPP (M = Cu, Zn, and Co) thin film into
polypropylene (PP) fibers by using different synthetic routes to
Figure 234. Schematic illustration of phase transformation of CdSe develop MOF-textile composites as chemically protective
QDs to CdS nanosheets in La-btc based nanocomposites with materials (Figure 238).1605 In all these cases, PP fiber is first
enhanced photoelectrochemical activity. Adapted with permission integrated into ZnO via atomic layer deposition (ALD)
from ref 1601. Copyright 2016 American Chemical Society. method. The formation of PP@Cu-TCPP composite using
hydroxy double salt (HDS) solid surface displays enhanced
trace concentrations of 1.29 and 2.22 pM within linear range of adsorption capacity toward NH3 by a factor of 3 in comparison
0.001 to 1.0 ng·mL−1. to conventional MOF powders as well as for 2-chloroethyl

Figure 235. Schematic diagram of the fabrication of electrochemical biosensing based on AuNCs@Zr-MOF-based nanosheets for detection of
cocaine, including (i) preparation of the 2D AuNCs@Zr-MOF nanosheets, (ii) immobilization of the aptamer strands, and (iii) detection of
cocaine. Reproduced with permission from ref 1602. Copyright 2017 American Chemical Society.

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Figure 236. Schematic diagram of the preparation process of Ti3C2Tx-Co-(1,4-bdc) hybrid for oxygen evolution reaction. Adapted with permission
from ref 1603. Copyright 2017 American Chemical Society.

integrate Mg−Al LDH nanosheets and Cu-btc nanocrystals has

been illustrated by Hwang et al. (Figure 239).1606 The
nanohybrid displayed improved hydrostability and humidity
adsorption, which manifested its use as water adsorbent.
6.3. Thin Film and Nanosheet Composites of 2D MOFs
with Organic Polymers
In recent times, the fabrication of 2D thin films and nanosheets
based composites via integration of 2D MOFs into organic
polymers matrices is another unique development achieved in
the field of composite materials. We will discuss few examples
in this context below.
Two lamellar microcrystalline 2D Cu(I)-thiophenolate
MOFs, CuCT (CT = 4-carboxy-thiophenolate) and CuMCT
(MCT = 4-methoxycarbonyl-thiophenolate), synthesized in
different organic solvents, acetone, and methanol, respectively,
and subsequently utilized for thin film composite formation
using polyvinylidene difluoride (PVDF) organic polymer have
been investigated by Delgado and co-workers.1607 Both
precursor MOFs and composite thin films exhibit reversible
luminescent thermochromic response (Figure 240). The fine-
tuning of these freestanding and robust stimuli responsive thin
films devoid of macroscopic defects can be deployed for
bioimaging sensory and other electronic/optoelectronic
devices. Similar thermoresponsive bright-yellow thin film
composite was also observed for Cu(I) based square-grid 2D
MOF Cu4I4(1,4-bix)2 incorporated in poly(methyl methacry-
late) (PMMA) acting as a colorimetric sensor.1608
Similarly, Moorthy et al. demonstrated the immobilization of
exfoliated 2D MOFs, which they termed as metal-organic
Figure 237. Diagrams highlighting the fabrication of MOF devices nanosheets (MONs) into polymer matrix.1609 [Cd2Cl2(DP)3]·
and sheet resistance of SOFT sensor devices. (a) Starting materials for (CHCl3)4(DMF)4·EtOH (Cd-DP) (DP = 4,4′-((2,2,7,7-
SOFT-sensors from organic triphenylene-based ligand (HHTP or tetraphenyl-2,7-dihydropyrano[2,3-g]chromene-5,10-diyl)bis-
HATP), metallic node (Ni(OAc)2, or NiCl2), and fabric swatch
(cotton shows no conductivity). Photograph of cotton swatch is
(ethyne-2,1-diyl))dipyridine) has been entrapped inside
shown. (b) Solvothermal condensation of these reagents in water ormosil polymer matrix to form the composite film. This
produces conductive SOFT devices: textiles coated with nanoporous also displayed thermal photochromic behavior from green to
MOF. Macroscopic through molecular level detail is shown, from a colorless reversible switching (Figure 241). Another example
photograph of cotton SOFT sensor postreaction (top, left), to of 2D MOF-polymer nanosheet composite is Cu-TCPP@PPy
scanning electron micrographs detailing MOF coating on fibers (PPy = polypyrrole) formed via in situ polymerization of
(bottom left) and characteristic MOF nanorod texture (bottom pyrrole.1610 This material shows improved flexible super-
right), to space-filling model of MOF (top, right). (c) Sheet resistance capacitor performance with storage capacity of ∼500 F g−1 at a
measurements for SOFT-swatches. Adapted with permission from ref
current density of 1 A g−1.
1604. Copyright 2017 American Chemical Society.
Gascon and co-workers illustrated the formation of Cu-(1,4-
bdc) MOF nanosheets using bottom-up diffusion-mediated
ethyl sulfide (CEES), a blistering agent simulant, in humid approach which was then fabricated into polyimide polymer
conditions with RH of 80%. matrix with varied 2−12 wt % filler loadings.1611 Finally, this
6.2.6. With Layered Double Hydroxide (LDH) Nano- was transformed into composite membrane to exhibit gas
sheets. The combined exfoliation and self-assembly route to separation ability toward CO2 from CO2/CH4 mixture.
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Figure 238. Schematic illustration of the metal−TCPP MOF growth on PP fibers via different synthetic routes. (a) ALD ZnO-treated PP (PP@
ZnO), (b) PP@Zn−TCPP, (c) PP@Cu−TCPP, (d) PP@HDS, and (e) PP@Cu−TCPP composites. Components of Cu−TCPP are illustrated in
the dashed box. Reproduced with permission from ref 1605. Copyright 2019 John Wiley & Sons.

Figure 239. Schematic diagram of an exfoliation−self-assembly route to Cu-btc MOF−LDH nanohybrids. Reproduced with permission from ref
1606. Copyright 2017 American Chemical Society.

Some Ag(I) based 2D MOFs embedded inside different activity towards Gram positive bacteria S. aureus compared to
organic polymer matrices have also been reported in the Gram negative bacteria E. coli.1613
literature.1612,1613 [Ag2(BPZ)] 2D MOF combined with PE 2D lanthanide MOFs were also employed for making
disks displayed antibacterial activity in fully reducing bacterial polymer composites.1614−1616 Imidazole ligand based Tb(III)
strains of Escherichia coli, Pseudomonas aeruginosa, and MOF, [Tb3(L)(μ3-OH)7]·H2O (L = N,N′-bis(acetoxy)-
biimidazole) was integrated into poly(methyl methacrylate)
Staphylococcus. aureus within 24 h.1612 Following the similar
(PMMA) matrix and developed into a stable and green
fabrication approach, 2D forms of [Ag2(Me4bpz)] (Me4bpz = emissive film composite.1615 It exhibited four times longer
3,3′,5,5′-tetramethyl-4,4′-bipyrazole) and [Ag(dpzm)(ClO4)] lifetime in comparison to its pristine MOF, which is
(dpzm = 2,2′-dipyrazinylmethane) complexes amalgamated anticipated due to OH oscillator and doped PMMA coupling
with PE and polycaprolactone to form thin film composites leading to radiative process via repression of multiphoton
were also reported and demonstrated better antibacterial relaxation. Similarly, Wang and co-workers utilized two
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composite material described by Lang et al. has been prepared

by a stepwise solid-state reaction between a cationic 2D MOF
[Ag6(Tab)6(bpe)2(MeCN)]2(PF6)12·6DMF·2MeCN based on
dodecanuclear [Ag12S12] cluster and an anionic dye Congo red
(Figure 243).1618 This MOF-CR composite displayed marked
properties, including amplified photovoltaics and upgraded
capacitor-based responses in juxtaposition to its parent MOF.
The same group also presented two more 2D MOF-dye
composites with cationic−anionic relationship like the above
example.1619 This involved [Zn3(bfps)(1,2,3-btc)2(H2O)6]·
4H2O and [Zn(bfps)(Hbtc)]·H2O MOFs in combination
with Orange IV dye to form the resultant MOF-OIV
composites (bfps = N 1 ,N 4 -bis(5-fluoropyridin-3-yl)-
succinamide). These two composites display intensified
photocurrent responses compared to their respective pristine
polymeric compounds. The above two examples from Lang’s
Figure 240. (top) Schematic diagram of the fabrication of MOF@ laboratory elucidated an efficient route to develop MOFs-dye
PVDF composites via drop casting. (bottom) Illustration of the composites with potential optoelectronics applications.
thermochromic behavior of CuCT@PVDF and CuMCT@PVDF thin
films: (a) Solid-state emission of CuCT@PVDF under ambient light 6.5. 2D Ordered Colloidal Array
and UV lamp excitation (λexc = 365 nm) at different temperatures. (b) The fabrication of MOFs within a 2D colloidal crystal array
Sequential pictures of CuCT@PVDF film during warming from 77 K (CCA) acting as a templating agent can lead to a facile
to room temperature under UV lamp excitation (λexc = 365 nm). (c) approach to obtain 2D nano thin film-based superstructures
Solid-state emission of CuMCT@PVDF under ambient light and UV
lamp excitation (λexc = 365 nm) at different temperatures. Adapted
with large surface area.1620 Such approach is akin to a
with permission from ref 1607. Copyright 2017 John Wiley & Sons. templated synthesis of 2D MOF thin film via asymmetric
growth process. The air−solution interfacial growth method
resulted in 2D CCA-ZIF-8 thin film, which shows potential
acetonitrile vapor sensing. The highly porous 2D ordered
macroporous (2DOM) MOF thin film was obtained by the
removal of 2D CCAs followed by loading of PVDF membrane
and deposition of spin-coated ZIF-8 nanoparticles (Figure
244). These 2DOM thin films were applied for removal of dyes
from aqueous solutions exhibiting highest retention rate for
methylene blue (MB). The entire work demonstrated the
methodical and effective pathway for designing multifunctional
MOF thin films with potential device applications.

7. SUMMARY AND OUTLOOK

Although the Hofmann clathrate was discovered in 1897, the
enormous growth of 2D MOFs is witnessed only recently. The
Figure 241. Schematic view of formation of Cd-DP MONs via
research activities on the majority of these 2D MOFs were of
exfoliation and integration into ormosil polymer with photochromic exploratory nature initially to recognize their network
response. Reproduced with permission from ref 1609. Copyright 2018 architectures and different types of entanglements and not
Elsevier. for their properties or applications, which began to emerge
only recently. In other words, this research area is currently
witnessing its next phase of growth from design and structures
isomorphic wavy lanthanide MOFs, [Ln(L)(NO 3 ) 3 ] n ·
to properties and applications. Researchers are interested in
2C4H8O2 (Ln = Eu, Tb; L = 2,2′-((2-(pyridin-4-yl)-2-((2-
discovering new and fascinating properties of these 2D MOFs
((thiophen-2-ylmethyl)carbamoyl)phenoxy)methyl)propane-
like mechanical, electrical (conductivity, semiconductivity,
1,3-diyl)bis(oxy))bis(N-(thiophen-2-ylmethyl) benzamide), to
pyroelectricity, piezoelectricity, and ferroelectricity, etc.),
develop PMMA doped polymer film composites.1616 The
optical (luminescence, birefringence, nonlinear optics, etc.),
EuL@PMMA composite exhibits near white-light emission
optoelectronic, magnetic, chiral separation, and catalytic
when excited at 296 nm, and both composites served as
properties. Fabrication of these 2D MOFs into nanosheets
luminescent ratiometric sensors for aqueous phase detection of
takes this area literally from the hands of chemists to physicists
Zn2+ ion (Figure 242).
and materials scientists. These highly crystalline materials are
Incorporation of a small amount of [Cu2(1,4-bdc)4] filler
very attractive due to the ease of formation by a single-pot self-
loading (2−4 wt %) enhance the selectivities of 6FDA-DAM
assembly method. Despite great progress in the field of 2D
polyimide and PIM-1 for the CO2/CH4 gases due to the
MOFs, challenges like large-scale production with high quality
molecular sieving effect.1617
and controlled structures still exist. The influence due to
6.4. Composites with Dyes intrinsic and extrinsic defects, which is very important for
While many MOFs exhibit electronic properties, especially as making useful devices, is yet to be understood thoroughly.
semiconductivity, the electronic properties of MOF-dye Now a large library of 2D MOFs with a variety of network
composites are less studied. An example of a 2D MOF-dye topologies and entanglements is available for making MOF-
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Figure 242. (a) Undulated 2D sheets of TbL in the ab-plane. (b) Emission spectra of EuL@PMMA and TbL@PMMA (c) excited at 309 nm upon
immersion in metal cations (0.1 M). (d) Photograph of EuL@PMMA (top) and TbL@PMMA (bottom) excited at 254 nm upon Zn2+ addition of
different concentrations under UV light. Adapted with permission from ref 1616. Copyright 2020 American Chemical Society.

Figure 243. Schematic representation of MOF-CR composite exhibiting (a) enhanced photocurrent and (b,c) dielectric properties. Adapted with
permission from ref 1618. Copyright 2019 Royal Society of Chemistry.

Figure 244. Illustration of the asymmetric growth of MOF thin films on 2D CCAs anchored at the air−solution interface and the fabrication of
2DOM MOF thin films. Reproduced with permission from ref 1620. Copyright 2016 American Chemical Society.

based devices. There is hope that the design strategies AUTHOR INFORMATION
discussed here for 2D MOFs provide access for making new Corresponding Author

MOFs with desired properties and opportunities to bring the Jagadese J. Vittal − Department of Chemistry, National
University of Singapore, Singapore 117543, Singapore;
chemists to the forefront of advanced materials along with orcid.org/0000-0001-8302-0733; Email: jjvittal@
u.nus.edu, [email protected]
materials researchers and technologists. This interdisciplinary
Authors
approach will push these 2D MOFs towards technologically
Gouri Chakraborty − Department of Chemistry, National
indispensable materials in the future. University of Singapore, Singapore 117543, Singapore
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In-Hyeok Park − Graduate School of Analytical Science and photophysical, and nonlinear optical behavior of MOFs and hybrid
Technology (GRAST), Chungnam National University, materials.
Daejeon 34134, South Korea; orcid.org/0000-0003- Jagadese J. Vittal after his B.Sc. (University of Madras) and M.Sc.
1371-6641 (Madurai University) received Ph.D. from Indian Institute of Science,
Raghavender Medishetty − Department of Chemistry, IIT Bangalore, in 1982. After working as a postdoctoral fellow at the
Bhilai, Raipur, Chhattisgarh 492015, India; orcid.org/ University of Western Ontario, Canada, he managed the X-ray facility
0000-0003-2289-2655 in the Department of Chemistry. In 1997, J.J. accepted a faculty
Complete contact information is available at: position at the National University of Singapore (NUS). He
https://pubs.acs.org/10.1021/acs.chemrev.0c01049 established the Service Crystallography Laboratory in the Department
of Chemistry. He is currently a Professor in the Department of
Notes Chemistry. He held a World Class University Chair Professorship at
the Gyeongsang National University, Jinju, South Korea (2009−
The authors declare no competing financial interest.
2013). J.J.’s current major research interests include various aspects of
Biographies coordination polymers and metal-organic frameworks, solid-state
chemistry, and solid-state photoreactivity. He co-authored “Crystal
Gouri Chakraborty earned her B.Sc. degree in Chemistry (Hons) EngineeringA Textbook” with G. R. Desiraju and A. Ramanan. He is
from St. Xavier’s College (Autonomous), Kolkata, in 2011 and M.Sc. a Fellow of the Royal Society of Chemistry, Singapore National
degree in Chemistry from the Indian Institute of Technology Roorkee Institute of Chemistry, and Indian Chemical Society. He holds
(IIT Roorkee) in 2013. Following this, she received her Ph.D. degree editorial board membership in several journals including ACS Crystal
in 2019 from the Department of Chemical Sciences, Indian Institute Growth & Design. He is the founder and organizing committee
of Science Education and Research Mohali (IISER Mohali), under the member of Singapore National Crystal Growing Challenge (1997−
supervision of Prof. Sanjay K. Mandal, where her work focused on the 2016).
design and development of luminescent coordination polymers and
metal-organic frameworks for sensing applications. Currently, she is
ACKNOWLEDGMENTS
pursuing her postdoctoral research in Prof. Jagadese J. Vittal’s
laboratory, with her research interests focused on the synthesis of We gratefully acknowledge the Ministry of Education,
coordination polymers and metal-organic frameworks and their Singapore, for the financial support through NUS Tier 1
properties. Grant R-143-000-B13-114. We sincerely thank Dr. Hong
Sheng Quah for his interest and help in this review at the initial
In-Hyeok Park is currently an Assistant Professor at the Graduate stage. R.M. thanks DST-SERB for the Start-up Research Grant
School of Analytical Science and Technology (GRAST), Chungnam SRG/2019/001508 and IIT Bhilai for RIG/2003600.
National University (CNU), Daejeon, South Korea. He received his
B.Sc. (2010) and Ph.D. degrees (2015) from the Department of ABBREVIATIONS
Chemistry, Gyeongsang National University (GNU), Jinju, South
Korea, under supervisions of Prof. Shim Sung Lee at GNU and Prof. 1,2-bdc = 1,2-benzenedicarboxylate
Jagadese J. Vittal at National University of Singapore (NUS), 1,3-bdc = 1,3-benzenedicarboxylate
Singapore. During his graduate study, he received a POSCO TJ 1,4-bdc = 1,4-benzenedicarboxylate
Park Doctoral Fellowship from the prestigious POSCO TJ Park 2,5-PDC = 2,5-pyridinedicarboxylate
Foundation. After receiving the Ph.D., he received an Excellent Ph.D. 1D = one-dimensional
Thesis Award from the Korean Chemical Society (2015). He also 2D = two-dimensional
received a prestigious S-OIL Excellent Thesis Award (Grand Prize)
3D = three-dimensional
from the Korean Academy of Science and Technology (KAST) and
2F-4spy/3F-4spy = 2′ or 3′-fluorostyrylpyridine
the Korean Association of University Presidents (2015). Prior to
4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene
joining CNU, he worked as a postdoctoral researcher with Prof. Shim
4bpdh = 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene
Sung Lee at GNU (2015−2016), Prof. Kian Ping Loh at NUS
4-spy = 4-styrylpyridine
5CH3O-BIm = 5-methoxybenzimidazole
(2016−2020), and Prof. Ok-Sang Jung at Pusan National University,
5Cl-BIm = 5-chlorobenzimidazole
Busan, South Korea (2020). His research interests focus on crystalline
5NO2-BIm = 5-nitrobenzimidazole
organic-inorganic hybrid materials such as metal-organic frameworks.
AIE = aggregation-induced emission
and hybrid perovskites.
azpy = trans-4,4′-azobis(pyridine)
Raghavender Medishetty is an Assistant Professor at the Indian bpdc = biphenyl-4,4′-dicarboxylate
Institute of Technology Bhilai, India. Previously, he completed his bpe = 1,2-bis(4-pyridyl)ethene
undergraduate and master studies at Osmania University, Hyderabad, bpea = biphenylethene-4,4′-dicarboxylate
and Banaras Hindu University, Varanasi, in India, respectively. He was bpeb = 1,4-bis[2-(4′-pyridyl)ethenyl]benzene
all-India topper in GATE-2009, a national competitive exam in India. bpee = 1,2-bis(4-pyridyl)ethane
Later he joined to do Ph.D. in the laboratory of Prof. Jagadese J. Vittal bpethy = 1,2-bis(4-pyridyl)ethyne
at the National University of Singapore, with the prestigious bpp = 1,3-bis(4-pyridyl)-propane
Presidential Graduate Fellowship. He received the outstanding bptc = biphenyl-2,4′,5-tricarboxylate
researcher award during his graduate studies. Later, he moved to bpy = 4,4′-bipyridine
Ruhr University, Bochum, Germany, as an Alexander von Humboldt BPZ = 4,4′-bipyrazole
post-doctoral fellow in 2014, followed by worked as postdoctoral btc/BTC = 1,3,5-benzenetricarboxylate
fellow at Technical University of Munich, Germany. He has also been btd = 1,10-bis(1,2,4-triazol-1-yl)decane
selected as the Rising Star in the Asian Crystallographic Association CIE = Commission Internationale de l’Eclairage
(AsCA) meeting, 2019. His current interests include photochemistry, COFs = covalent-organic frameworks
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