Cobalt-Salen-Based Porous Ionic Polymer: The Role of Valence on Cooperative Conversion of CO₂ to Cyclic Carbonate

Cobalt-salen-based porous ionic polymers, which are composed of cobalt and halogen anions decorated on the framework, effectively catalyze the CO₂ cycloaddition reaction of epoxides to cyclic carbonates under ambient conditions. The cooperative effect of bifunctional active sites of cobalt as the Lewis acidic site and the halogen anion as the nucleophile responds to the high catalytic performance. Moreover, density functional theory results indicate that the cobalt valence state and the corresponding coordination group influence the rate-determining step of the CO₂ cycloaddition reaction and the nucleophilicity of halogen anions.