Synthesis of Polycarboxylate Rhodium(II) Metal–Organic Polyhedra (MOPs) and their use as Building Blocks for Highly Connected Metal–Organic Frameworks (MOFs)

Abstract

Use of preformed metal‐organic polyhedra (MOPs) as supermolecular building blocks (SBBs) for the synthesis of metal‐organic frameworks (MOFs) remains underexplored due to lack of robust functionalized MOPs. Herein we report the use of polycarboxylate cuboctahedral RhII‐MOPs for constructing highly‐connected MOFs. Cuboctahedral MOPs were functionalized with carboxylic acid groups on their 12 vertices or 24 edges through coordinative or covalent post‐synthetic routes, respectively. We then used each isolated polycarboxylate RhII‐MOP as 12‐c cuboctahedral or 24‐c rhombicuboctahedral SBBs that, upon linkage with metallic secondary building units (SBUs), afford bimetallic highly‐connected MOFs. The assembly of a pre‐synthesized 12‐c SBB with a 4‐c paddle‐wheel SBU, and a 24‐c SBB with a 3‐c triangular CuII SBU gave rise to bimetallic MOFs having ftw (4,12)‐c or rht (3,24)‐c topologies, respectively.

Beyond structural motifs: the frontier of actinide-containing metal–organic frameworks

“… 259–272 Overall, actinide integration inside a framework lattice could expand the realm of catalytic transformations currently dominated by transition metal-based MOFs and lead to new reactive pathways (through stabilization of unique oxidation states of actinides) or lower activation energy barriers. 47–49,259–272 However, as clearly seen from this section, none of these benefits, as a result of integration of actinides in the MOF lattice, have been demonstrated extensively yet. Therefore, expanding the currently explored routes, that traditionally rely on lanthanides or transition metals, is crucial since it could lead to unexpected results that arise from the unique electronic behavior and possibly reveal cooperative reactivity of actinide-based catalytically active metal nodes and surrounding organic ligands.…”

“…Since MOFs can be considered as “bulky linkers” for stabilization of elusive oxidation states, as it was shown on the example of transition metal-based MOFs, 47–49 it is also important to pursue this direction for actinide-containing frameworks. For example, the coordination of actinides in molecular complexes can lead to the stabilization of less-common oxidation states ( e.g.…”

Coordination polymers with embedded recognition sites: lessons from cyclotriveratrylene-type ligands

“…13 pre-formed coordination cages of any type into crystalline MOF or coordination polymer materials are rare. 38 Postsynthetic organisation of coordination cages can also target soft materials. 39 Coordination polymer networks with available CTV-ligand binding sites also occur where more complicated cage-like assemblies are formed within the network.…”

Linking metal–organic cages pairwise as a design approach for assembling multivariate crystalline materials

“…1b). 24 These methodologies however, are limited to only one type of MOC as the buildingblock. 25,26 The coordinative linking of two different MOCs represents a significant advancement in the design of multifunctional porous solids, but is hitherto unrealized.…”