Metallocorrole-based porous organic polymers as a heterogeneous catalytic nanoplatform for efficient carbon dioxide conversion

Metallocorrole macrocycles that represent a burgeoning class of attractive metal-complexes from the porphyrinoid family, have attracted great interest in recent years owing to their unique structure and excellent performance revealed in many fields, yet further functionalization through incorporating these motifs into porous nanomaterials employing the bottom-up approach is still scarce and remains synthetically challenging. Here, we report the targeted synthesis of porous organic polymers (POPs) constructed from custom-designed Mn and Fe-corrole complex building units, respectively denoted as CorPOP-1(Mn) and CorPOP-1(FeCl). Specifically, the robust CorPOP-1(Mn) bearing Mn-corrole active centers displays superior heterogeneous catalytic activity toward solvent-free cycloaddition of carbon dioxide (CO₂) with epoxides to form cyclic carbonates under mild reaction conditions as compared with the homogeneous counterpart. CorPOP-1(Mn) can be easily recycled and does not show significant loss of reactivity after seven successive cycles. This work highlights the potential of metallocorrole-based porous solid catalysts for targeting CO₂ transformations, and would provide a guide for the task-specific development of more corrole-based multifunctional materials for extended applications.