“Orthogonal‐Twisted‐Arm” Ligands for The Construction of Metal–Organic Frameworks (MOFs): New Topology and Catalytic Reactivity

Abstract Extended tetratopic benzoic acid ligands with “orthogonal‐twisted‐arms” conformations were designed and synthesized for the construction of new MOF structures (OTA‐MOF). Upon coordination with Cd 2+ and Cu 2+ cations, two well‐defined new MOFs were prepared. X‐ray single crystal structures were successfully obtained, demonstrating the formation of a new topology (4,4,4‐c). The OTA2‐MOF‐Cu gave moderate stability in organic solvents and good gas sorption ability toward CO 2 . This new MOF showed superior catalytic reactivity toward the epoxide‐CO 2 cycloaddition, giving >50 folds yield enhancement over the controlled reaction without MOF. It is expected that this new ligand design, porous structure, and excellent CO 2 catalytic reactivity will make OTA‐MOF promising new materials for applications in catalysis and separation.