Poly(ionic liquid)s for Photo‐Driven CO(2) Cycloaddition: Electron Donor–Acceptor Segments Matter

CO(2) cycloaddition with epoxides is a key catalytic procedure for CO(2) utilization. Several metal‐based catalysts with cocatalysts are developed for photo‐driven CO(2) cycloaddition, while facing difficulties in product purification and continuous reaction. Here, poly(ionic liquid)s are proposed as metal‐free catalysts for photo‐driven CO(2) cycloaddition without cocatalysts. A series of poly(ionic liquid)s with donor–acceptor segments are fabricated and their photo‐driven catalytic performance (conversion rate of 83.5% for glycidyl phenyl ether) outstrips (≈4.9 times) their thermal‐driven catalytic performance (17.2%) at the same temperature. Mechanism studies confirm that photo‐induced charge separation is promoted by the donor–acceptor segments and can accelerate the CO(2) cycloaddition reaction. This work paves the way for the further use of poly(ionic liquid)s as catalysts in photo‐driven CO(2) cycloaddition.