A Pyridinium‐Pyridinium Zinc(II) Porphyrin Ion Porous Organic Polymer as Efficient Heterogeneous Catalyst for Cycloaddition of Epoxides with CO2

Abstract

AbstractA zinc(II)porphyrin‐based ion porous organic polymer (ZnTPyPBr4‐iPOP) is successfully synthesized from newly designed pyridinium‐functionalized cationic Zn‐porphyrin monomer (ZnTPyPBr4) by free radical self‐polymerization, and is employed as an efficient bifunctional heterogeneous catalyst for CO2 cycloaddition reaction with epoxides. The ZnTPyPBr4‐iPOP exhibits excellent catalytic performance and good substrate expansion in CO2 cycloaddition reaction under solvent‐free and cocatalyst‐free conditions with a TOF as high as 15,500 h−1 for the cycloaddition of CO2 and epichlorohydrin. The synergistic effect of zinc(II)porphyrin as the Lewis acidic site and the Br− anion as the nucleophile in ZnTPyPBr4‐iPOP responds to the high catalytic activity. Moreover, ZnTPyPBr4‐iPOP can easily be recovered and reused at least seven times without the loss of activity. This work provides a valuable approach for the synthesis of novel and efficient heterogeneous catalyst for CO2 cycloaddition.