Water‐Resistant Defective iMOFs via Halogen Coordination for CO 2 Capture and Size‐Selective Cycloaddition

Abstract A bottom‐up ligand engineering strategy enables the construction of ionic metal‐organic frameworks (iMOFs) with hierarchical porosity and abundant unsaturated Cu+ active sites via halogen anion coordination. These iMOFs exhibit exceptional water stability due to a unique Cu ─ Br stabilization mechanism. The defect‐engineered frameworks demonstrate enhanced CO 2 adsorption, efficient humid CO 2 capture, and superior catalytic performance in CO 2 ‐epoxides coupling reaction, exhibiting size‐selectivity correlated with their pore dimensions.