Phenyl Benzo[b]phenothiazine as a Visible Light Photoredox Catalyst for Metal‐Free Atom Transfer Radical Polymerization

Abstract This paper reports use of phenyl benzo[ b ]phenothiazine (Ph‐benzoPTZ) as a visible light‐induced metal‐free atom transfer radical polymerization (ATRP) photoredox catalyst. Well‐controlled polymerizations of various methacrylate monomers were conducted under a 392 nm visible light LED using Ph‐benzoPTZ to activate different alkyl halides. The use of the photocatalyst enabled temporal control over the growth of polymer chains during intermittent on/off periods. The polymerization was initiated and progressed only under stimulation by light and completely stopped in the absence of light. Block copolymers were synthesized to demonstrate high retention of chain end fidelity in the polymers and livingness of the process.