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d3ma00477e

This Perspective article reviews recent advancements in the self-assembly of metal-organic cages (MOCs) and their connections for CO2 remediation applications. By linking MOCs through various bonding methods, novel materials with enhanced porosity and mechanical properties are created, outperforming single MOCs in CO2 capture. The article emphasizes the challenges in structural characterization of these materials and their potential in applications requiring adaptability to different shapes.

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3 views11 pages

d3ma00477e

This Perspective article reviews recent advancements in the self-assembly of metal-organic cages (MOCs) and their connections for CO2 remediation applications. By linking MOCs through various bonding methods, novel materials with enhanced porosity and mechanical properties are created, outperforming single MOCs in CO2 capture. The article emphasizes the challenges in structural characterization of these materials and their potential in applications requiring adaptability to different shapes.

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iamanand1920
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Materials

Advances
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PERSPECTIVE View Journal | View Issue

Connecting metal–organic cages (MOCs) for


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CO2 remediation
Open Access Article. Published on 05 September 2023. Downloaded on 6/26/2025 6:00:53 PM.

Cite this: Mater. Adv., 2023,


4, 4333
Javier Martı́-Rujas

In this Perspective article, recent developments in the self-assembly of supramolecular porous materials
made of zero-dimensional (0D) porous metal organic cages (MOCs), connected by different approaches,
and their application in CO2 remediation are reviewed. The connection of MOCs carried out by
coordination-bond driven linking, covalent bond linking and mechanical bond formation, leads to the
formation of novel smart materials ranging from solid to gel states of matter, and in some cases, porous
materials with hierarchical porosity stemming from the intrinsic MOC porosity and the voids generated
among the connected MOCs. Both porosities can be tuned depending on the MOC sizes and on the way
the cages are connected (i.e., coordination-driven and covalent bond linking). In general, the
supramolecular, often networked, materials arising from the connection of MOCs tend to show diffuse
scattering, denoting only short-range order, making their structural elucidation very challenging or simply
not possible. Thus, the bulk structure of materials formed by connected MOCs is often deduced from
information obtained through other techniques like powder XRD, pair distribution function (PDF) analysis,
solid-state NMR, dynamic light scattering (DLS), and positron annihilation lifetime spectroscopy (PALS).
Materials obtained upon the connection of MOCs are usually in the form of amorphous solids, gels, xerogels
and porous liquids (PLs) but have shown to outperform the CO2 capacity and improved mechanical
properties when compared to the single MOCs. The preparation of materials at the interface between solids
and liquids is important to create functional materials displaying unique properties such as porosity in liquids
and gels arising from the MOCs and their networked assembly, hence allowing CO2 gas diffusion into the
cage’s voids where CO2 can be trapped or catalytically transformed into other molecules (i.e., formic acid
Received 28th July 2023, (HCOOH)). Thus, materials containing connected MOCs can be exploited where MOFs cannot be used due
Accepted 31st August 2023 to their brittle nature, typical of solid crystalline materials, for instance in applications where the porous
DOI: 10.1039/d3ma00477e material has to fit to different shapes for example those required to fit in tubes or shapes that usually
crystalline solids cannot adapt easily, thus expanding the applications of connected MOC materials in areas
rsc.li/materials-advances involving fluids.

1. Introduction organic ligands and metal ions or clusters of metals (called


secondary building units or SBUs) ‘‘stuck’’ together by coordi-
Combustion of fossil fuels, such as natural gas, petroleum, and nation bonds.4–8 MOFs are also regarded as coordination
coal in order to meet the energy demands of our past and polymers or coordination networks. The possibility of synthe-
recent societies, has contributed to an atmospheric rise in sizing porous MOFs and fine-tuning their porosity has given
carbon dioxide (CO2), and hence the Earth’s temperature the chance to exploit such materials for gas adsorption, and in
increases due to the greenhouse effect.1 The rise of atmo- particular MOFs and MOF-based materials have emerged as
spheric CO2 is threatening the Earth equilibrium including good candidates to capture CO29 and are also suitable for CO2
the natural environment and the human society. Therefore, transformation into other molecules that are not harmful to the
technologies on carbon capture and conversion approaches are environment.2
being proposed to decrease the CO2 atmospheric emission.2,3 MOF’s structural properties including porosity, designabi-
Metal organic frameworks (MOFs) as post zeolitic materials lity, crystallinity, flexibility and well-defined structures
are highly crystalline materials obtained by self-assembling obtained from single crystal X-ray diffraction data (SC-XRD)10
and powder X-ray diffraction data (powder XRD)11 have con-
Dipartimento di Chimica Materiali e Ingegneria Chimica. ‘‘Giulio Natta’’,
tributed to the rapid advancement of MOFs as functional
Politecnico di Milano, Via L. Mancinelli 7, 20131 Milan, Italy. materials for CO2 remediation.9 The atomic resolution 3D
E-mail: [email protected] crystal structure allows not only the direct visualization of the

© 2023 The Author(s). Published by the Royal Society of Chemistry Mater. Adv., 2023, 4, 4333–4343 | 4333
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Perspective Materials Advances

interior of the pores and their surfaces, but also the in situ 3D internal voids.15–19,28 Crucially, the size and shape of the
observation of chemical intermediates in reactions that in tradi- MOCs can be tuned by choosing ligands with various sizes and
tional solution reactions cannot be isolated.12–14 Hence, concerning shapes which in combination with transition metals can give rise
gas adsorption, the availability of an X-ray crystal structure gives the to different metal organic polyhedric structures. This was devel-
opportunity to better understand where the CO2 molecules can be oped by several research groups15,16,19,21,22 and a seminal con-
adsorbed. Crucially, 3D X-ray crystallographic analysis is funda- tribution has been the work by Fujita,29 which used pyridinic
mental to perform a combined theoretical–experimental structural ligands and encapsulated Pd(II) and Pt(II) salts to block the
analysis on CO2 adsorption of a given porous material allowing polymerization towards MOFs formation (i.e., Cd(NO3)5,29 vs.
rationalization of the adsorption process.9 (en)Pd(NO3)2),30 thus constraining the self-assembling products
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

Another class of hybrid metal organic materials are the so- towards discrete structures (convergent way) including squares,30
Open Access Article. Published on 05 September 2023. Downloaded on 6/26/2025 6:00:53 PM.

called metal organic cages (MOCs)15–22 (also known as metal cages31 and bowls.32 In general, the polyhedric structures are
organic polyhedra (MOPs)), that are porous structures used in highly symmetric and are classified as Archimedean or Platonic
many applications such as in molecular sensing,23 stabilization solids.26 Recently new trends have been developed to synthesize
of unstable species,20,21 and catalysis18 but also for CO2 capture less symmetric MOCs to mimic the asymmetric binding pockets
and transformation.24 MOCs are discrete (0D) structures with where enzymes carry on biocatalytic reactions in proteins.33
well-defined internal voids that can be exploited as host–guest The increased interest in MOCs research is because they offer a
systems. In the solid-state, MOCs must maintain their internal wide variety of host–guest chemistry applications taking advan-
voids to efficiently use their host–guest properties, for instance tage of the internal space of the nanocages which can be used as a
in heterogeneous gas–solid reactions where the cages are the nanocontainer in relevant industrial applications.15,18,20,21 This is
solid phases used to trap CO2. especially important because molecules in a confined space can
The focus of this Perspective article is not on isolated MOCs, show a different behavior from that observed in the bulk solution
but on materials that are formed by ‘‘connected’’ MOCs25–27 as and unusual reactions can be carried out within the cages.18,34
this linking of MOCs yields functional novel materials like Also, the internal space of the cages can be chemically functio-
amorphous polymeric porous MOCs, supramolecular gels, nalized to create specific binding sites that can be used for
aerogels and porous liquids (PLs) for CO2 applications (vide molecular recognition in such a way that can be applied for
ante). Unusual physical phenomena ranging from controlled trapping gas molecules such as H2, N2 or CO2 as small gases,
microporosity in soft matter yielding soft supramolecular but also volatile organic compounds (VOCs) such as large aro-
materials which are flexible and permanently porous, at the matic compounds, drug molecules or macromolecules like
interface between solids and liquids, have been recently proteins35 just to mention a few.
reported. The strategy of linking MOCs is interesting because Much of the work involving MOCs is being done in solution
it exploits the MOC’s properties while also combining features because the self-assembled cages are stable in the liquid media,
of new materials.25–27 Usually, the new materials formed after and in particular in water,36 in which many host–guest pro-
linking the single MOCs display properties that belong to soft cesses can be monitored by solution NMR spectroscopy. On the
matter rather than pure solids which have led to the design of other hand, working with MOCs in the solid-state, for instance
self-healing porous polymers and materials targeted for drug in the molecular recognition of aromatic guests, the trapping of
delivery.27 Reviews about MOCs linked in different ways such as small gases like CO2, or in the study of catalytic reactions, the
chemical bonds including coordination and covalent bonds integrity (i.e., porosity) of the metal–organic cages should be
using organic molecules, or mechanical bonds forming poly- maintained. The stability of the MOC’s architecture is funda-
meric structures of MOCs are very few25–27 and reviews of such mental if the cages must be used in separation applications
materials for CO2 adsorption and fixation are nonexistent to the such as CO2 adsorption because they need to be activated. That
best of our knowledge. Therefore, this Perspective article will be is to create the empty space, by removing the guest component
of interest to many researchers working on the host–guest (usually a solvent used for the crystallization), which has the
chemistry of polymerized MOCs covering a wide range of areas role of templating agent.31 Importantly, in the activation pro-
going from fundamental to the applied sides of materials cess also water and/or solvent molecules coordinated to metal
sciences. centers are removed, which can lead to uncoordinated metal
atoms (nodes) that are used as catalytic reaction sites. However,
upon thermal treatment, MOCs might collapse and therefore
2. Metal organic cages (MOCs) as host lose the intrinsic porosity and hence their potential function as
molecular adsorbents. This structural collapse must be avoided
structures for inclusion properties in if the guest molecules should be included in the MOCs.
supramolecular materials formed of
2.1. Different strategies to link MOCs for CO2 applications
connected MOCs
MOCs can be defined as ‘‘macromolecules’’ because of their
MOCs are hybrid metal–organic materials self-assembled with discrete (0D) nature and, in many cases are defined as porous
metal ions and organic ligands which do not form extended due to their internal voids and gas adsorption abilities. In the
structures but discrete zero-dimensional (0-D) complexes with crystalline state, electrostatic interactions hold MOCs together,

4334 | Mater. Adv., 2023, 4, 4333–4343 © 2023 The Author(s). Published by the Royal Society of Chemistry
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giving them a periodic nature. Thus, it can be envisaged that their new supramolecular materials formed by connected MOCs
inherent porosity might be maintained if monomeric MOCs are showed that CO2 can be adsorbed outperforming the CO2 adsorp-
linked together through organic ligands in a supramolecular tion capacity and catalytic activity of non-connected MOCs. More-
structure. However, the probability to obtain the linked MOCs over, the overall stability and flexibility of the linked MOCs is also
in a crystalline and ordered state is difficult. On the other hand, it enhanced with respect to the original molecular MOCs.
is also important to design strategies leading to porous materials
that behave more like soft matter rather than crystalline (i.e., rigid 2.2. The low crystallinity of solid materials formed of
structure), because soft mater materials can be used in applica- connected MOCs and their structural characterization
tions in the liquid or gel states. Therefore, not only to increase the The preparation of large supramolecular entities, such as those
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

MOCs’ stability and flexibility, but to explore the formation of new arising from the connection of MOCs, often in between the
Open Access Article. Published on 05 September 2023. Downloaded on 6/26/2025 6:00:53 PM.

and large supramolecular entities, strategies such as linking solid and liquid states (i.e., soft matter), yields solids that are
MOCs via coordination of bridging ligands to unsaturated metal poorly crystalline, with only short-range order, or just amorphous,
sites; connecting the 0D cages upon covalent bond formation; or by in which the absence of Bragg diffraction does not allow full
interlocking MOCs using mechanical bonds, have been recently structure determination using single crystal X-ray diffraction (SC-
developed (Fig. 1). XRD)10 or powder XRD structure solution.11 The entrapment of
Two MOCs can be connected in different manners. In the next crystallization solvent inside the MOCs or in the spaces generated
examples the synthetic approaches shown in Fig. 1 have been between the connected cages, tend to form amorphous materials.
applied to crosslink MOCs. In this way, polymeric structures made It is important to mention that in some cases, depending on the
of discrete MOCs are produced. This strategy uses MOCs for way the self-assembly takes place such as when fast crystallization
obtaining supramolecular polymers with different types of poros- processes are required to control the crystallization product (i.e.,
ities (i.e., hierarchical porosity) generated from intrinsic micropor- crystallization under kinetic control), often result as microcrystals
osity inside the cage cavity and mesoporosity between the cages or amorphous phases which complicates the structure elucidation
generated after the linkage of the MOCs (Fig. 1). by SC-XRD (vide ante).
Crucially, the mesoporosity will depend also on the length, the The impossibility in the understanding of the 3D atomic
flexibility and shape of the linker molecule connecting the MOCs. arrangement in the self-assembled material does not allow us
The bulk porous nature of the material can be used for trapping to make efficient progress in the design and fine tuning for
CO2 or for transforming CO2 into non-harmful substances. The improving the properties of materials made of connected
MOCs. Thus, understanding their functional properties with-
out detailed structural characterization is often very challen-
ging. However, techniques such as X-ray diffraction (SAXS), pair
distribution function (PDF) analysis, combined with solution
and solid-state NMR, dynamic light scattering (DLS), and
positron annihilation lifetime spectroscopy (PALS) can be used
to gain information on the supramolecular superstructure
formed upon linking MOCs.
Despite the difficulties in the structural characterization of
some of the supramolecular materials obtained by connecting
monomeric MOCs, a myriad of new properties were discovered,
such as softness and processability of porous materials, making
the effort of studying new avenues of assembling individual
MOCs into polymeric materials worth exploring. As most
porous materials are used in the solid-state, they cannot be
used in common flow processes. Supramolecular MOC poly-
mers displaying characteristic features of liquid or liquid-like
materials such as gels27 are clearly interesting with huge
potential in industrial applications.

3. Polymeric structures generated by


linking MOCs with ligands via
coordination bonds
3.1. Formation of a supramolecular solid polymer connecting
MOCs via coordination bonds with hierarchical porosity
Fig. 1 Cartoon showing the stepwise synthesis of connected MOCs via
ligand coordination (top), covalent bond formation from functionalized An example showing how MOCs can be connected through
MOCs (middle) and interlocking of MOCs via mechanical bonds (bottom). covalent bonds using bidentate ligands was reported in 2011 by

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Chun and Moon in which 2,7-napthalenedicarboxylate and materials (hierarchical porosity) whose porosities can be tuned
Cu2+ were self-assembled into a large MOC with 12 Cu–Cu by selecting different cages and linkers. In this way, the
paddlewheel units, [Cu24(2,7-ndc)24(DMF)10(H2O)14 (MOC-1).37 preparation of supramolecular hybrid metal organic materials
The SC-XRD structure was determined by synchrotron radiation that are more in the regime of soft-matter (i.e., supramolecular
and the self-assembled material is a 3.3 nm cuboctahedron polymers with intrinsic (micro)porosity) than conventional
(Archimedean solid) as shown in Fig. 2. In the crystalline state, solid MOFs or MOCs can be synthesized.
the cuboctahedrons are in close contact with adjacent ones via
the triangular windows packing in a body-centered cubic struc- 3.2. Synthesis of a supramolecular porous aerogel (SAG) for
ture (Im3% m space group). The MOC is very large with its 68% of CO2 adsorption connecting MOCs through coordination bonds
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space occupied by solvent molecules, which is 22 147 Å3 of its When thinking about materials used as adsorbents, what
Open Access Article. Published on 05 September 2023. Downloaded on 6/26/2025 6:00:53 PM.

total unit cell volume. The cuboctahedron can be considered comes to mind are solid crystalline materials which are brittle,
nearly spherical with an internal diameter of an imaginary such as MOFs. Porous materials displaying properties like
sphere of 1.8 nm (Fig. 2a) falling in the microporous regime. processability and softness are important as they can be used
The as synthesized MOC-1 is crystalline but becomes amor- in applications where crystalline, rigid, and porous MOFs
phous in the activation process, upon evacuation of guests, cannot be exploited. Furukawa and co-workers using deriva-
because they act as templating agents. However, the amor- tives of the highly stable cuboctahedral MOC [Rh2(bdc)2]12
phous phase of MOC-1 shows an amorphous-to-crystalline (AC) (MOC-2)38 (where H2bdc – benzene-1,3-dicarboxylic acid) self-
transformation once it traps guest molecules. MOC-1 can trap assembled using a dirhodium paddlewheel motif and a dicar-
CO2 which shows reversible type I isotherms without signifi- boxylic acid (Fig. 3a) could synthesize amorphous soft porous
cant hysteresis because only the internal voids of amorphous materials.39 Because of the different lability among equatorial
MOC-1 (microporous regime) are available for gas inclusion.37 (poorly labile) and apical (highly labile) dirhodium paddle-
One approach to see if there is an increase in CO2 adsorption, wheel atoms in the MOC-2, the cages can be linked via
with respect to isolated MOC-1, can be carried out by synthesiz- coordination bonds using appropriate ligands (vide ante). The
ing a polymeric structure of connected MOC-1, but the intrinsic icosahedral MOC-2 has high structural stability upon desolva-
porosity of individual MOCs must be maintained. tion and guest removal due to the Rh–Rh single bond and
The linkers used to connect the MOC-1 were diamine strong Rh–carboxylate coordination bond.
spacers with different lengths and flexibility such as ethylene- The authors demonstrated how a supramolecular MOC
diamine (en), xylenediamine (xn) and diaminoheptane (hn) polymer obtained by linking a derivative dirhodium MOC-3,
(Fig. 2b). Crosslinking such ligands with MOC-1, results in a in which H2bdc ligand is substituted by 5-dodecoxybenzene-
porous material that has two pore regimes: the intrinsic MOC 1,3-dicarboxylic acid = H2bdc-C12 to increase its solubility,
belonging to the microporous regime and the one created using linkers with two imidazole functionalities (Fig. 4).40 To
among the linked cages, the mesoporous regime. The supra- polymerize the C12RhMOP monomers (MOC-3), the imidazole
molecular material with ethylenediamine linker shows some linker 1,4-bis(imidazole-1-ylmethyl)benzene (bix) was used. The
crystallinity while the solid materials including xylenediamine addition (stepwise) of bix into a DMF solution of MOC-3 was
and diaminoheptane are amorphous phases. This is probably monitored by dynamic light scattering (DLS) giving a maximum
due to the higher flexibility of xn and hn. of particle sizes of 78 nm that were revealed to be spherical as
Interestingly, CO2 sorption experiments at 195 K and 1 bar shown by field emission scanning electron microscopy
are systematically lowered in going from purely microporous (FESEM). Larger particles can be obtained adding less molecu-
MOC-1 to mesoporous materials MOC-1(en), MOC-1(xn) and lar equivalents of bix. Powder XRD experiments show that the
MOC-1(hn). This behavior is explained as the adsorption of spherical particles are amorphous as no Bragg diffraction is
small gases is favoured in micropores showing strong fluid wall observed.
interactions. Although the mesoporous materials did not per- Kinetic control in the synthesis of porous extended MOF
form better than MOC-1 for CO2 adsorption, this example structures41–43 and MOCs44,45 has been proved to be a good
demonstrates the potential to prepare bimodal porous strategy to selectively obtain the desired products. In this vein,
applying kinetic control by excess of bix molecules to a MOC-3
solution and cooling from 80 1C to room temperature, it was
possible to isolate a MOC monomer with the (C12RhMOC)-
(bix)12 composition of 5.2  1.2 nm size. After 1d, no aggrega-
tion was observed by keeping the suspension at room tempera-
ture. Because all the coordination sites are occupied by bix
ligand, the only way to link the cages is by heating the solution
containing the isolated MOCs (fully coordinated with bix) in
order to release bix ligands and thus trigger the polymerization
Fig. 2 (a) Single crystal XRD structure of the cuboctahedral MOC-1.37
of (C12RhMOC)(bix)12 into larger particles of 22  7 nm. The
(b) Chemical reaction of MOC-1 with the diamine spacers used to form the supramolecular colloidal gel (SCG) was obtained upon incuba-
supramolecular material made of connected MOC-1.37 tion (Fig. 3b). The macromolecular polymeric structure of

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Crucially, the uptake at P/P0 = 0.95 of SAG-1 is superior to that


observed for the porous monomer with 68.64 cm3 g 1 and
40.23 mol CO2/mol C12RhMOC vs. 46.01 cm3 g 1 and 22.20 mol
CO2/mol C12RhMOC respectively. Thus, using kinetic control, it
is possible to prepare a supramolecular material with two
different macroscopic morphologies including spherical MOCs
particles and 3D interconnected colloidal gels.

3.3. Synthesis of a supramolecular porous aerogel (SAG) for


This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

photocatalytic reduction of CO2 into formic acid


Open Access Article. Published on 05 September 2023. Downloaded on 6/26/2025 6:00:53 PM.

As mentioned, one efficient method to reduce the amount


of CO2 gas is by transforming it into molecules that can be
used in other applications.46 The versatility of SAG-1 has
also been exploited as a heterogeneous catalyst in the photo-
catalytic reduction of carbon dioxide into formic acid
(HCOOH).47 Crucially, the catalytic activity was better than
the single MOCs paddlewheel complexes and other heteroge-
neous photocatalysts.
Fig. 3 (a) Structure of the C12RhMOF porous monomer (MOC-3) For the catalytic study, the authors exploited both MOCs,
obtained from the related [Rh2(bdc)2]12 crystal structure formed by rho- MOC-2 and MOC-3, using isophthalic acid and 5-dodecoxy-
dium ions (green) coordinated to the oxygen atoms (red) of H2bdc-C12 benzene-1,3-dicarboxylic acid respectively, and by using bix
ligand in gray, with the appended aliphatic chain simplified as a purple the MOCs were self-assembled into supramolecular polymers
sphere. (b) Gel and (c) aerogel obtained from the connection of mono-
in the form of colloids or gels depending on the quantity of bix
meric MOC-3. (d) CO2 adsorption isotherm at 195 K of SAG-1 (red),
supramolecular MOC polymer (blue), supramolecular MOC polymer of used. Unfortunately, the supramolecular polymers are amor-
bigger dimensions (green) and C12RhMOP (black). Adsorption and phous showing only short-range order.
desorption experiments are represented with filled and empty symbols Interestingly, both the colloidal and the gel evidenced
respectively. Reproduced from ref. 40. catalytic activity for the transformation of CO2 into formic acid
as the only product. Both C12Rh-CPP (colloid) and C12Rh-SAG
show the same catalytic activity (TOF = 59 h 1) despite having
different morphology. Importantly, the catalytic activity is a bit
higher than the molecular building block C12RhMOC (TOF =
52 h 1). To understand the catalytic behavior, pristine C12RhMOC
was functionalized with monodentate 1-benzylimidazole (bnix)
to yield [Rh2(C12-bdc)2]12(bnix)12 (C12RhMOCbnix) to mimic the
external surface of the MOCs in C12Rh-CPP and C12Rh-SAG
(Fig. 4). Interestingly, the catalytic activity is increased with
values very similar to those observed in the supramolecular
structures with linked MOCs. From those results, first, the
Fig. 4 Cartoon showing the functionalization of Rh-MOC (0D) with bnix
ligand to mimic the external surface of supramolecular colloid C12Rh-CPP authors concluded that the catalytic activity is not limited to
and gel C12Rh-SAG. Reproduced from ref. 47 with permission from ACS, surface effects in the heterogeneous polymers and, second, that
copyright 2022. the internal part of the cages is accessible to the reactants. The
presence of the coordinated bix and bnix ligands slightly
increases the electron density around the Rh centers, resulting
linked MOCs did not form sufficient electrostatic interactions in an increase in the catalytic activity.
to pack the building components in an ordered manner, The self-assembled supramolecular catalysts have demon-
resulting in an amorphous phase as shown by powder XRD. strated high TOF up to 60 h 1 outperforming by 30% the
The porosity of the supramolecular polymer was evidenced RhMOC and other state-of-the-art heterogeneous photocatalyst
by CO2 gas adsorption by transforming first the SCG to the systems including Rh-MOFs by at least a factor of 12. The
aerogel (treated with supercritical CO2 and then heating in the optimal catalytic activity has been rationalized because of the
vacuum) SAG-1 (where SAG = supramolecular aerogel). SAG-1 high number of Rh atoms per gram of the catalyst but also
was composed of a hierarchical microporous structure of fused favoured by the accessibility inside the supramolecular cage.
particles of 38  11 nm in size (Fig. 3c). Structural aspects focussing on the inter-atomic distances
The supramolecular material contains a robust RhMOC between atoms were determined using PDF analysis, regarding
backbone with permanent microporosity in an amorphous the stability of the MOCs linked by bix ligands. Both samples,
state. The intrinsic porosity of MOC-3 is preserved after poly- pristine and spent samples show that the G(r) curves demon-
merization as shown by the type I isotherm at 195 K (Fig. 3d). strate that at the molecular level, there is no distortion or

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decomposition of the paddlewheel Rh sites at the Rh–Rh nodes


in the MOC and no presence of Rh0 species was detected.

3.4. Synthesis of a supramolecular porous aerogel IL by


connecting MOCs via coordination bonds and its CO2
adsorption capacity
The integration of porous liquids (PLs) in the fabrication of gels
can yield new functional materials displaying new properties
arising from the combination of porosity and structural tun-
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ability. Functional gels combine properties of solids and


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liquids which so far have been synthesized using microporous


MOCs,48 metal–organic frameworks (MOFs),49 and covalent-
organic frameworks (COFs).50 They become porous after sol-
vent removal forming porous aerogels but they lose the initial
gel properties. To avoid the loss of gel–liquid properties (soft
materials) whilst maintaining the porous properties, PL-like
Fig. 5 (a) CO2 uptake isotherms of Gel_IL at different concentrations of
gels or porous gels are supposed to be a promising alternative
MOC-2 networks at 303 K under 100 kPa. (b) Particle size distribution of
to PLs for some useful applications. Gel_IL with different concentrations of MOC-2 networks derived from
More recently, the exploitation of MOC-2 gel has been PALS experiments. (c) Cartoon representing the CO2 gas diffusion pathway
reported, through guest exchange, during which the original within the wet sample of connected MOCs. Reproduced from ref. 51 with
DMF guests are replaced by the ionic liquid (IL) 1-butyl-3- permission from ACS, copyright 2023.

methylimidazolium tetrafluoroborate ([BMIM]+[BF4] ).51 The


IL is too large to enter in the cage cavities once the gel is
adsorption increases too, showing that the MOC network is
activated but it enters into the hierarchichal porosity (i.e., the
accessible in the wet gel state. To investigate more deeply the
larger pores). Upon heating, the solvents can be removed giving
porosity of Gel_IL, positron annihilation lifetime spectroscopy
the obtained ionic liquid gel accessible microporosity with
(PALS) experiments were performed as it allows the detection of
good CO2 performances. The liquid exchange process is possi-
voids in liquid samples. Exposing the ionic liquid sample to a
ble due to the robust nature of the MOCs that maintain the gel
positron source like 22Na generates the ortho-positron (i.e., a
structural properties (i.e., it does not deform or collapse). The
parallel spin complex between e+ and e ). Measuring the
new material is claimed to be in between porous solids and
lifetime of o-positron it is possible to estimate the pore dis-
porous liquids. The new pore-networked gels have an increased
tribution size (PDS) of the liquid sample. That is, larger pores
gas sorption capacity as a result of the accessible porosity in the
correspond to slower decay rates and hence longer lifetimes.
MOC network.
The pore size distribution in the wet Gel_IL by measuring the
The rhodium-based cuboctahedral MOC-2, [Rh2(bdc)]12
lifetime of the o-positron was ca. 2.7 ns corresponding to a pore
(bdc = benzene-1,3-dicarboxylate) was selected for the porous
size of ca. 0.68 nm (Fig. 5b), which is the size in between the
building block for the formation of gel networks as it has 12
MOC network (solid aerogel) and that of the ionic liquid
available coordination sites at each axial position of the dirho-
[BMIM]+[BF4] . Increasing the concentration of the MOC net-
dium paddlewheel moiety for further coordination-driven
work does not increase the PDS but decreases the intensity of
crosslinking, and its thermal stability yields structural integrity
the peak due to lower mobility of the gel in the concentrated
under harsh activation conditions. To link the MOCs by coor-
gel. The CO2 uptake in the gel material follows the solution-
dination bonds and the gel formation, the bidentate ligand 1,4-
diffusion model (Fig. 5c), where the guest CO2 molecules reach
bis(imidazole-1-ylmethyl)benzene (btx) was used.
the interior of the connected MOCs. Thus, even in the wet state
The Gel_IL microporosity was measured using CO2 adsorp-
the supramolecular material is porous.
tion. The microporous of the MOCs were filled with DMF or
acetone used in the self-assembling process, which are
removed upon heating at 120 1C in a vacuum overnight. After
the thermal treatment, the material did not collapse, and the 4. From MOCs to polymers: covalent
porosity of the supramolecular structure was tested by CO2 cross-linking of MOCs to form
adsorption at 303 K. The isotherms were compared with the IL supramolecular flexible MOC materials
[BMIM]+[BF4] . As shown in Fig. 5a, neat IL has a lower
adsorption capacity compared to all the Gel_IL tested (i.e., with 4.1. Connecting MOCs by covalent bond formation for CO2
different concentration of MOC networks). adsorption
The CO2 sorption at ca. 100 kPa in the gel with 1.8 wt% A different strategy to link MOCs, to those observed so far, was
adsorbed 0.044 mmol CO2 per gram sample which is almost reported by Shimizu and co-workers by using the modified Cu24
two times larger than that of pure [BMIM]+[BF4] . If the MOC cuboctahedral Cu24 isophthalate by attaching in the 5-
concentration of MOC-2 in the gel is increased then the CO2 position of the isophthalate linkers in the external part of the

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presence of additional voids is a result of the cross-linking


process, and this allows for a higher CO2 adsorption in the solid
with ‘‘connected’’ MOCs than the single MOC-4. Interestingly,
CO2 adsorption at 298 K shows the same trend as seen for the
195 K experiments only with a slight decrease in the uptake
of CO2 of 2.3 mmol g 1 for MOC  40 and 1.3 mmol g 1 for
MOC-4 (Fig. 7b).
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5. From MOCs to polycatenanes or


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Fig. 6 (a) Synchrotron single crystal X-ray structure of MOC-4 displaying


the core MOC as the disordered alkyl chains could not be resolved [n]-catenane networks
crystallographically. (b) Cartoon depicting the cross-linking process via
G2 Grubb’s catalyst in DCM. Reproduced from ref. 52 with permission 5.1. Linking MOCs via mechanical bonds to form
from ACS, copyright 2019. polycatenanes made of cages
The last approach to connecting MOCs in a polymeric manner
cages with long alkyl chains having terminal alkenes (MOC-4) outlined in this Perspective is by linking them not by coordina-
(Fig. 6a).52 Using olefin metathesis reactions, the functiona- tion bonds, or by covalent bonds as recently seen, but by
lized MOC-4 were then connected. In the new synthesized mechanical bonds.53–56 Although studies of CO2 adsorption in
system, the MOCs are bridged by –OC18H34O– units among poly-catenanes formed of interlocked MOCs are very few,57
the isophthalate ligands (Fig. 6b). Synchrotron single crystal X- clearly the intriguing structural properties of cage-catenanes
ray crystallography revealed the structure which shows that the make such materials potential candidates for exploitation in
Cu24 metals linked by the organic ligand yield a cuboctahedral CO2 remediation. Polycatenanes made of rings (i.e., not by
of ca. 2 nm packing in the Pnnm space group. MOCs) can be defined as mechanically linked polymers derived
The MOC structure remains stable when dissolved in from catenane subunits. The mechanical properties of cate-
organic solvents but not in water. The functionalized MOC nanes are important because the individual ring components in
were linked via olefin metathesis using Grubb’s second- the catenane can have rotations, twisting and elongation move-
generation catalyst (G2) by solubilizing the cage in DCM under ments giving the mechanical molecule important functional
atmosphere conditions. In this work, three MOC-4 cross-linked properties.56 In order to separate two rings in a catenane it is
versions with E20%, E40% and E80% degrees of cross- necessary to break chemical bonds even though they are not
linking were studied. The three products referred to as MOC- connected via chemical bonds. If instead of using rings for the
4  20, MOC-4  40 and MOC-4  80 were indicated by solution formation of the catenane chains, MOCs are used, then cage-
1
H NMR. Upon crosslinking, the solid (MOC-4  40) and (MOC- catenanes or cage-polycatenanes can be generated.58,59 How-
4  80) appeared from the solutions in common organic ever, the synthesis of the cage-catenanes is challenging because
solvents (i.e., DCM, chloroform, ethyl acetate, THF and DMF) several aspects must be considered for appropriate cage
as microcrystalline samples (Fig. 7a). The partial solubility of interlocking.
MOC-4  20 suggested that the cross-linking reaction did not First, the size and number of windows and the size of the
proceed sufficiently due to inhomogeneous local cross-linking. cavity should be large enough to allow the formation of the
The most homogeneously cross-linked MOC-4 solid mechanical bond.59 Second, suitable metal atoms with a cer-
(MOC-4  40) was used for CO2 gas adsorption experiments tain lability are needed for the error checking in the reversible
at 195 K/1.2 bar, and adsorbed 2.18 mmol g 1 of CO2 while coordination bond formation involving intermediate struc-
monomeric MOC-4 adsorbed 1.16 mmol g 1. Thus, the tures. Third, the presence of guest molecules that act as
templating agents are needed to obtain crystalline
structures.59 Fourth, depending if the catenation is forming
1D-chains, 2D layers or 3D cage catenation, the electrostatic
forces keeping the chains or layers will influence their crystal-
linity, their dynamic behavior upon external stimuli, and hence
the gas adsorption properties. Thus, catenanes formed of
interlocked MOCs is another degree of structural complexity.

5.1. Mechanically interlocked tetrahedral M6L4 MOCs


yielding 3D cage polycatenanes
The example of Lu and co-workers reported a polycatenane self-
assembly of tetrahedral MOCs prepared using six [NiL]2+
Fig. 7 (a) Powder XRD patterns of the MOC-4 and the supramolecular
cross-linked products. (b) CO2 adsorption experiments carried out at 195 K
cations (where L = 1,4,8,11-tetraazaundecane) and four tri(4-
and 1.2 bar. Reproduced from ref. 52 with permission from ACS, copyright carboxy-benzyl)amine ligand (H3tcba) (Fig. 8a and b).57 The
2019. crystal structure was determined using an initial model

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structure of interlocked icosahedral M12L8 nanocages which


have huge internal voids of ca. 2700 Å3. So far, the work done on
such materials has been using the tridentate and rigid ligands
2,4,6-tris-(4-pyridyl)pyridine (TPP),61,62 (MOC-6) and 2,4,6-tris-
(4-pyridyl)benzene (TPB),44,45,63–65 (MOC-7) in which one single
icosahedral M12L8 nanocage is interlocked by two adjacent
cages forming 1D chains along the c-crystallographic direction
(Fig. 9a). Single crystals of the M12L8 poly-[n]-catenanes are
stable at room temperature and have shown to behave dyna-
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mically upon external stimuli. In particular, the heterogeneous


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gas–solid adsorption of aromatic molecules via molecular


recognition, has been demonstrated by multiple single-
crystal-to-single-crystal reactions.66 However, CO2 adsorption
has not yet been tested for such materials involving MOC-7. The
mechanically interlocked material shown in Fig. 9b might show
CO2 uptake.
Fig. 8 (a) Structure of cation [NiL]2+ and (b) ligand H3tcba used for self-
So far, such MOC-7 within the polymeric structures can be
assembling MOC-5. (c) Space-filling and (d) ball-and-stick representations
of two interlocked MOC-5 nanocages, showing the interlocked corners in
suitable for gas adsorption because they are interlocked in the
face-to-face stacking fashion with a distance of 6.219 Å between two absence of solvent molecules. It has been demonstrated that
nitrogen atoms of two tcba3 . A single cage is interlocked by other four the amorphous phase of the M12L8 poly-[n]-catenane can
cages (not shown). (e) Sorption isotherms of N2, H2 and CO2 for dehy- adsorb, from the gas phase, aromatic molecules as evidenced
drated mechanically interlocked MOC-5. Reproduced from ref. 57.
by powder XRD analysis, thus indicating a significant dynamic
behavior of the non-ordered phase containing the interlocked
obtained from SC-XRD but refined using powder XRD data by M12L8 nanocages.63 It has also been demonstrated that in a
Rietveld refinement as suitable crystals for SC-XRD were not heterogeneous solid–liquid phase process, methanol can be
available. Four tcba3 anions link six [NiL]2+ cations via its trapped in the amorphous nanocages producing a swelling
three carboxy-benzyl groups leading to tetrahedral cages with effect on the material.63 Thus, CO2 could also be entrapped
the formula [NiL]6(tbca)4 (MOC-5). In MOC-5, each Ni(II) is six- in the interlocked MOC-7 cages.
coordinated to four N atoms from L and two carboxylate O
atoms from two individual tcba3 anions, and each tcba3
connects three [NiL]2+. The MOC is formed of four tcba3
anions located at the vertexes of the cage and six Ni(II) metals
situated at the edges of the cage resulting in a M6L4 nanocage
(Fig. 8c and 8d). The size of the cage considering the distances
among edges is 16.64 Å. In the center of the cage there is a
ClO4 anion. The solvent accessible volume is ca. 10% of the
total unit cell volume. The large openings of the M6L4 MOC-5
nanocages allows a quadruple catenation in which one cage is
mechanically interlocked with another four through all its four
vertices (Fig. 8d). The overall structure is a 3D extended poly-
catenane remaining one of the few of such structures
reported.60
Gas adsorption experiments show that the polycatenane
formed of interlocked tetrahedral cages is nonporous for CO2
at 195 K (Fig. 8e), because it becomes amorphous upon guest
water release (activation process). However, it shows that for
small alcohols such as methanol, ethanol i-propanol and i-
butanol it is porous. The sorption isotherms show that the
smaller the alcohol the better the adsorption capacity per cage.
Thus, after interlocking of the tetrahedral MOCs there is
enough space for adsorbing gas molecules (i.e., alcohols).

5.2. Mechanically interlocked icosahedral M12L8 MOCs Fig. 9 (a) Interlocking of three M12L8 nanocages expanding along the
yielding 1D cage polycatenanes c-axis. To differentiate the individual M12L8 cages the carbon atoms
are green, yellow and orange. (b) View of the isolated voids in the
Another type of poly-[n]-catenane structure that can be a M12L8 MOCs after manually removing the solvent molecules. Reproduced
potential candidate for CO2 adsorption is the 1D chain from ref. 45.

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6. Benefits of linking MOCs for CO2 the CO2 adsorbed is superior when the cages are connected
remediation compared to the monomer MOCs not forming part of the
supramolecular polymer. Photocatalytic CO2 reduction to for-
The beneficial aspects of synthesizing new materials by con- mic acid has been shown to work well in a supramolecular
necting MOCs for CO2 remediation are numerous and impor- aerogel of connected MOCs. Gel-like materials prepared by
tant ranging from structural to functional aspects. The most connecting MOCs can be exploited in applications where MOFs
salient features described in this article are highlighted below. cannot be used due to their brittle nature, typical of solid
First, the crosslinking of MOCs gives the possibility of crystalline materials. Semi-solid materials like gels containing
synthesizing porous materials with hierarchical porosity strongly connected MOCs are processable, soft, and can be
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including microporosity and mesoporosity with applications shaped and used for instance in application shapes that usually
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in CO2 remediation that can outperform those of isolated crystalline solids cannot adapt easily, thus expanding the
MOCs. applications of connected MOCs materials in areas involving
Second, the formation of supramolecular metal–organic fluids. Mechanically interlocked tetrahedral MOCs have been
architectures upon connecting MOCs yields materials that are tested also for CO2 adsorption. Despite not showing CO2 uptake
soft-mater-like materials such as supramolecular porous gels they can take up other small molecules like alcohols. Larger
and aerogels which find applications in areas involving fluids. interlocked cages such as M12L8, due to their dynamic beha-
Third, as shown, the CO2 uptake performance of MOC-3 is viour upon external stimuli, are potential candidates which are
preserved after cross-linking (i.e., the original porous properties worth trying in applications of CO2 remediation. The potential
of MOC-3 are maintained) and in SAG-1 the CO2 uptake at of linking different types of MOCs using coordination driven,
P/P0 = 0.95 is higher compared to that of the isolated MOC-3 covalent linking or mechanical bonds, into supramolecular
(40.23 mol CO2/mol C12RhMOC (SAG-1) vs. 22.20 mol CO2/mol porous materials, really shows how versatile this research area
C12RhMOC (MOC-3)) showing the benefit of connecting iso- is. Supramolecular materials including linked MOCs, like the
lated MOC-3. ones reviewed in this Perspective, will soon produce novel
Fourth, improved photocatalytic reduction of CO2 into materials with unexplored functional properties not only in
formic acid using the supramolecular aerogel SAG-1 is CO2 remediation but in many other applications from regen-
significantly improved, outperforming by 30% that of single erative medicine to soft robotics.
MOCs paddlewheel complexes and other heterogeneous
photocatalysts.
Fifth, novel materials that are between porous solids and
Author contributions
porous liquids can be synthesized (by connecting MOC-2 with J. M.-R. conceived and wrote the article.
the introduction of IL in the mesopores), showing about double
CO2 sorption capacity at ca. 100 KPa when compared to the IL.
This is explained due to the accessible porosity in the soft Conflicts of interest
material of connected MOCs.
There are no conflicts to declare.
Sixth, using a different cross-linking mechanism by covalent
bond formation, and not by means of coordination bonds as in
the previous cases, linked MOC-4 (at 192 K/1.2 bar) shows Acknowledgements
improved gas uptake of 2.18 mmol g 1 of CO2, while mono-
meric MOC-4 adsorbed 1.16 mmol g 1. J. M.-R. thanks Politecnico di Milano for funding (Fondo
Mechanically interlocked MOCs are far less explored for CO2 Chiamata Diretta Internazionalizazzione. Prg. Id. 61566).
adsorption, but the dynamic behavior and the internal voids
left after the MOC’s interlocking show potential in CO2 reme- Notes and references
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