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PERSPECTIVE View Journal | View Issue
CO2 remediation
Open Access Article. Published on 05 September 2023. Downloaded on 6/26/2025 6:00:53 PM.
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.
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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
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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
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MOCs’ stability and flexibility, but to explore the formation of new arising from the connection of MOCs, often in between the
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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.
© 2023 The Author(s). Published by the Royal Society of Chemistry Mater. Adv., 2023, 4, 4333–4343 | 4335
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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
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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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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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