Designed porosity in coordination materials often relies on highly ordered crystalline networks, which provide stability upon solvent removal. However, the requirement for crystallinity often impedes control of higher degrees of morphological versatility, or materials processing. Herein, we describe a supramolecular approach to the synthesis of amorphous polymer materials with controlled microporosity. The strategy entails the use of robust metal–organic polyhedra (MOPs) as porous monomers in the supramolecular polymerization reaction. Detailed analysis of the reaction mechanism of the MOPs with imidazole-based linkers revealed the polymerization to consist of three separate stages: nucleation, elongation, and cross-linking. By controlling the self-assembly pathways, we successfully tuned the resulting macroscopic form of the polymers, from spherical colloidal particles to colloidal gels with hierarchical porosity. The resulting materials display distinct microporous properties arising from the internal cavity of the MOPs. This synthetic approach could lead to the fabrication of soft, flexible materials with permanent porosity.

Metal-organic polyhedra (MOPs) are ultra-small (typically 1 nm to 4 nm) porous coordination cages made from the self-assembly of metal ions and organic linkers and amenable to the chemical functionalization of its periphery; however, it has been challenging to implement post-synthetic functionalization due to their chemical instability. Herein, we report the use of coordination chemistries and covalent chemistries to post-synthetically functionalize the external surface of 2.5 nm stable Rh(II)based cuboctahedra through their Rh-Rh paddlewheel units or organic linkers, respectively. We demonstrate that 12 N-donor ligands, including amino acids, can be coordinated on the periphery of Rh-MOPs. We used this reactivity to introduce new functionalities (e.g. chirality) to the MOPs and to tune their hydrophilicity/hydrophobic character, which allowed us to modulate their solubility in diverse solvents such as dichloromethane and water. We also demonstrate that all 24 organic linkers can be postsynthetically functionalized with esters via covalent chemistry. In addition, we anticipate that these two types of post-synthetic reactions can be combined to yield doubly-functionalized Rh-MOPs, in which a total of 36 new functional molecules can be incorporated on their surfaces. Likewise, these chemistries could be synergistically combined to enable covalent functionalization of MOPs through new linkages such as ethers. We believe that both reported post-synthetic pathways can potentially be used to engineer Rh-MOPs as scaffolds for applications in delivery, sorption and catalysis.

The upbuilding of dirhodium tetracarboxylate paddlewheels into porous architectures is still challenging because of the inertness of equatorial carboxylates for ligand-exchange reaction. Here we demonstrate the synthesis of a new family of metal-organic cuboctahedra by connecting dirhodium units through 1,3-benzenedicarboxylate and assembling cuboctahedra as porous solids. Carbon monoxide and nitric oxide were strongly trapped in the internal cavity thanks to the strong affinity of unsaturated axial coordination sites of dirhodium centers.

Kawano and colleagues show two distinct ion conductance states by embedding a single metal-organic porous molecule with Archimedean cuboctahedron geometry into a planar lipid bilayer. The triangular and square apertures in the cuboctahedron work independently as ion-transporting pathways. By changing the aliphatic chain length introduced on the periphery of the cuboctahedron, the authors identified that the rotational dynamics of the cuboctahedron regulate the open pore time of each conductance state through distinct apertures and the switching between them.

Graphite oxide was prepared by oxidation of graphite using the Hummers method, and its ultrasonication in water yielded dispersed graphene oxide (GO) sheets. These sheets were then crosslinked with a water soluble polymer, namely poly (allylamine) hydrochloride (PAH), by cabodiimide coupling. Free standing composite films were obtained by filtration. These crosslinked composites showed better mechanical properties than unmodified GO films and those of composites that were made by simple mixing of GO and PAH. The filtration process was optimized to produce strong GO films which were subsequently crosslinked with PAH in-situ to produce very strong composites with tensile strengths up to146 MPa.

Porous molecular cages have a characteristic processability arising from their solubility, which allows their incorporation into porous materials. Attaining solubility often requires covalently bound functional groups that are unnecessary for porosity and which ultimately occupy free volume in the materials, decreasing their surface areas. Here, a method is described that takes advantage of the coordination bonds in metal–organic polyhedra (MOPs) to render insoluble MOPs soluble by reversibly attaching an alkyl‐functionalized ligand. We then use the newly soluble MOPs as monomers for supramolecular polymerization reactions, obtaining permanently porous, amorphous polymers with the shape of colloids and gels, which display increased gas uptake in comparison with materials made with covalently functionalized MOPs.

Assemblies of lantern-type metal–organic polyhedra are found to show gate-opening gas adsorption depending on how they are treated with solvents.

Various synthetic routes to 2-isopropyl-4-methoxyphenol 3, the phenol core of Gefapixant citrate (MK-7264), are described, which provide better alternatives to the initial four-step supply route. These new routes include a coumarin fragmentation approach in flow, a rhenium-catalyzed isopropylation of mequinol, and a bromination/methoxylation of 2-isopropylphenol. After exploring several approaches, a robust two-step process for the preparation of 3 from the commodity starting material 2isopropylphenol was developed. The optimized route employs a highly regioselective bromination. After isolating the bromophenol DABCO cocrystal, a copper-catalyzed methoxylation delivers 3 in high yield. This route is successfully demonstrated at the plant scale with low process mass intensity and cost.