Highly Robust {In 2 }-Organic Framework for Efficiently Catalyzing CO 2 Cycloaddition and Knoevenagel Condensation.

To improve the catalytic performance of metal-organic frameworks (MOFs), creating higher defects is now considered as the most effective strategy, which can not only optimize the Lewis acidity of metal ions but also create more pore space to enhance diffusion and mass transfer in the channels. Herein, the exquisite combination of scarcely reported [In 2 (CO 2 ) 5 (H 2 O) 2 (DMF) 2 ] clusters and 2,6-bis(2,4-dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (H 5 BDCP) under solvothermal conditions generated a highly robust nanoporous framework of {[In 2 (BDCP)(DMF) 2 (H 2 O) 2 ](NO 3 )} n ( NUC-65 ) with nanocaged voids (14.1 Å) and rectangular nanochannels (15.94 Å × 11.77 Å) along the a axis. It is worth mentioning that an In(1) ion displays extremely low tetra-coordination modes after the thermal removal of its associated four solvent molecules of H 2 O and DMF. Activated {[In 2 (BDCP)](Br)} n ( NUC-65Br ), as a defective material because of its extremely unsaturated metal centers, could be generated by bromine ion exchange, solvent exchange, and vacuum drying. Catalytic experiments proved that the conversion of epichlorohydrin with 1 atm CO 2 into 4-(chloromethyl)-1,3-dioxolan-2-one catalyzed by 0.11 mol % NUC-65Br could reach 99% at 65 °C within 24 h. Moreover, with the aid of 5 mol % cocatalyst n -Bu 4 NBr, heterogeneous NUC-65Br owns excellent universal catalytic performance in most epoxides under mild conditions. In addition, NUC-65Br , as a heterogeneous catalyst, exhibits higher activity and better selectivity for Knoevenagel condensation of aldehydes and malononitrile. Hence, this work offers a fresh insight into the design of structure defect cationic metal-organic frameworks, which can be better applied to various fields because of their promoted performance.