Photoactive Complex Enabled Photo-controlled RAFT Polymerization with CF3 Radical

Recent advances in photo-controlled reversible addition-fragmentation chain-transfer (RAFT) polymerization have largely focused on the developments of initiators and chain-transfer agents. In this work, we report a photocatalytic platform enabling photo-controlled RAFT polymerization of acrylate-based monomers. The system employs readily accessible N-heterocyclic nitrenium as the photocatalyst, commercially available CF₃SO₂Cl as the CF₃ radical source, and a bis(trithiocarbonate) disulfide as the chain-transfer agent. This approach leverages a photoactive complex formed between the N-heterocyclic nitrenium and CF₃SO₂Cl to initiate polymerization, enabling polymerization with precise molar mass control and low dispersity.