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

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 CO2 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 CO2 with an excellent activity and good recyclability under mild conditions. Interestingly, these CO2 -philic materials could catalyze the cycloaddition reaction smoothly by using simulated flue gas (15 % CO2 in N2 , 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 CO2 .