Two-in-One: Photothermal Ring-Opening Copolymerization of CO₂ and Epoxides

A two-in-one strategy for the photothermal ring-opening copolymerization (PROCOP) of carbon dioxide (CO₂) and epoxides was developed by using visible light as an external stimulus. This strategy bridges two processes involving light-to-heat conversion and the alternating copolymerization of CO₂ and epoxides. As a proof-of-concept, aluminum porphyrin complexes were explored as photothermal catalysts to afford the copolymerization of CO₂/epoxides under a 635 nm laser irradiation. We demonstrated photothermally enhanced polymerization activity, in which the polymerization initiated by the photothermal effect showed a much higher turnover frequency than in the thermal system. Moreover, the PROCOP demonstrated a spatial-temporal control by a light on/off switch. This study provides a fascinating photothermal strategy not only for the CO₂/epoxides copolymerization but also for the ring-opening (co)polymerization of other cyclic monomers.