From UV to NIR: A full spectrum metal-free photocatalyst for efficient polymer synthesis in aqueous conditions.

Photo-mediation offers unparalleled spatiotemporal control over controlled radical polymerizations (CRP). Photo-induced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization is particularly versatile due to its oxygen tolerance and wide range of compatible photocatalysts. In recent years, broadband- and near-infrared (NIR)-mediated polymerizations have been of particular interest due to their potential for solar-driven chemistry and biomedical applications. In this work, we present the first example of a novel photocatalyst for both full broadband- and NIR-mediated CRP in aqueous conditions. Well-defined polymers were synthesized in water under blue, green, red, and NIR light irradiation. Exploiting the oxygen tolerant and aqueous nature of our system, we also report PET-RAFT polymerization at the microliter scale in a mammalian cell culture medium.