[Zn4O] Cluster‐Based Metal‐Organic Frameworks as Catalysts for Conversion of CO2

One unique two‐dimensional (2D) Zn‐MOF {Na[Zn_1.5(μ₄‐O)(L)]}_n ( 1 ) was synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction. Four Zn atoms are bridged through μ₄‐O to form [Zn₄O] clusters, which are further linked to form a 2D layer network through sharing Zn as vertexes. 1 exhibits high thermal stability up to 280 °C and keeps stable in common solvents and water solutions with pH ranging from 1 to 13. The catalytic studies reveal that compound 1 exhibits excellent catalytic activity for cycloaddition of CO₂ with epoxides into cyclic carbonates under mild conditions. Furthermore, 1 demonstrates good generality in CO₂ coupling reaction with extensive epoxides. Importantly, 1 can be reused for at least five times without significant reduction in catalytic ability.