Krista P. Balto and Joshua S. Figueroa Mixed-metal metal organic frameworks (MOFs) are attractive candidates for heterogeneous catalysis as they allow two metal centers with different reactivity profiles to be in close proximity within a solid-state lattice. Incorporation of multiple metal centers in network materials can be achieved using a variety of methods, including post synthetic modification, metal-ion exchange and the utilization of metalloligands. For most mixed-metal MOFs, incorporation of low-valent metal centers is difficult using these methods, since they preferentially bind to electronically “soft” ligands according to hard/soft Lewis acid/base theory. As a new approach to the formation of mixe-metal MOFs, we have explored the concept of electronic differentiation within linker group topologies. The electronically differentiated, sterically encumbering m-terphenyl isocyanide/carboxylate heteroditopic linker ligand 1,4-CNArMes2C6H4CO2H (TIBMes2H; TIB = terphenyl isocyanide benzoate; ArMes2 = 2,6-(2,4,6-Me3C6H2)2C6H2) is capable of selectively binding low-valent metals via the isocyano group as well as complexation of hard Lewis acidic metals through the carboxylate unit. In this presentation, the preparation and properties of new MOFs are discussed that specifically utilize the electronically soft isocyanide binding group as a key element in the design of mixed-metal network materials.

Mixed-metal coordination networks from an electronically differentiated isocyanide-carboxylate linker group

ACS Spring 2022

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