Fully meta‐Substituted 4,4′‐Biphenyldicarboxylate‐Based Metal–Organic Frameworks: Synthesis, Structures, and Catalytic Activities

Fully meta‐substituted 2,2′,6,6′‐tetramethoxy‐4,4′‐biphenyldicarboxylic acid (H2L) was synthesized and applied in the construction of three metal–organic frameworks (MOFs), {[Cu3L3(H2O)2(DMF)]n (1), [Zn4OL3]n (2), and [Zn4OL3(H2O)(DEF)]n (3)}. For 1, the approximately vertical twist of two benzene rings in L leads to the formation of a twofold‐interpenetrated 3D structure with 1D open channels (11 × 15 Å). MOFs 2 and 3 have classical twofold‐interpenetrated isoreticular MOF structures, and reversible transformation of the oxozinc carboxylate clusters of 2 and 3 could be realized via a solvent‐exchange‐induced single‐crystal‐to‐single‐crystal pathway, which provides direct structural evidence for a Zn4O core as Lewis acidic site in MOFs. Desolvated framework 1′ exhibits high permanent porosity (Langmuir surface area = 555 m2/g), high thermal stability (up to 300 °C), and highly active catalytic properties for cyanosilylation and olefin epoxidation. MOF 2 exhibits moderate carbon dioxide uptake ability and can efficiently catalyze the cycloaddition of CO2 with epoxides under mild conditions.