Red-Light-Induced, Copper-Catalyzed Atom Transfer Radical Polymerization

Despite advances in photochemical atom transfer radical polymerization (photoATRP), these systems often rely on the use of UV light for the activation/generation of the copper-based catalytic species. To circumvent the problems associated with the UV light, we developed a dual photoredox catalytic system to mediate photoinduced ATRP under red-light irradiation. The catalytic system is comprised of a Cu catalyst to control the polymerization via ATRP equilibrium and a photocatalyst, such as zinc(II) tetraphenylporphine or zinc(II) phthalocyanine, to generate the activator Cu^I species under red-light irradiation. In addition, this system showed oxygen tolerance due to the consumption of oxygen in the photoredox reactions, yielding well-controlled polymerizations without the need for deoxygenation processes.