Tuning the Catalytic Activity of Covalent Metal‐Organic Frameworks for CO2 Cycloaddition Reactions

Abstract The development of efficient, recyclable and low‐cost heterogeneous catalysts for conversion of carbon dioxide (CO 2 ) into epoxides is highly desired, yet remain a challenge. Herein, we have prepared three two‐dimensional (2D) copper(I) cyclic trinuclear units (Cu(I)‐CTUs) based covalent metal–organic frameworks (CMOFs), namely JNM‐13 , JNM‐14 , and JNM‐15 , via a one‐pot reaction by combination of coordination and dynamic covalent chemistry. Among them, JNM‐15 contained the highest density of copper catalytic sites, and exhibited the highest capacity for adsorption of CO 2 . More interestingly, JNM‐15 delivered the highest catalytic activity for cycloaddition of CO 2 to epoxides with good yields (up to 99 %), good substrate compatibility (11 examples) and reusability (four catalytic cycles) under mild condition.