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 (CO2) 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 CO2. More interestingly, JNM‐15 delivered the highest catalytic activity for cycloaddition of CO2 to epoxides with good yields (up to 99 %), good substrate compatibility (11 examples) and reusability (four catalytic cycles) under mild condition.