Charged Metalloporphyrin Polymers for Cooperative Synthesis of Cyclic Carbonates from CO2 under Ambient Conditions

Abstract A facile and one‐pot synthesis of metalloporphyrin‐based ionic porous organic polymers (M‐iPOPs) was performed through a typical Yamamoto–Ullmann coupling reaction for the first time. We used various characterization techniques to demonstrate that these strongly polar Al‐based materials (Al‐iPOP) possessed a relatively uniform microporosity, good swellable features, and a good CO 2 capture capacity. If we consider the particular physicochemical properties, heterogeneous Al‐iPOP, which bears both a metal active center and halogen anion, acted as a bifunctional catalyst for the solvent‐ and additive‐free synthesis of cyclic carbonates from various epoxides and CO 2 with an excellent activity and good recyclability under mild conditions. Interestingly, these CO 2 ‐philic materials could catalyze the cycloaddition reaction smoothly by using simulated flue gas (15 % CO 2 in N 2 , v / v ) as a raw material, which indicates that a stable local microenvironment and polymer swellability might promote the transformation. Thus, the introduction of polar ionic liquid units into metalloporphyrin‐based porous materials is regarded as a promising new strategy for the chemical conversion of CO 2 .