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 owing 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 owing 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