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

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