Visible-Light Photocatalytic Oxidation of DMSO for RAFT Polymerization

The solvent is an important, yet often forgotten part of a reaction mechanism. Many photochemical polymerizations are carried out using dimethyl sulfoxide (DMSO) as a way to promote the solubility of both the reactants and products, but its reactivity is rarely considered when initiation mechanisms are proposed. Herein, the oxidation of DMSO by an excited-state quinone is used to form initiating radicals resulting in the polymerization of methacrylate monomers, and the polymerization can be controlled with the addition of a chain transfer agent. This process leads to the formation of polymers with narrow molecular weight distribution, and the polymerization is able to be carried out in the presence of oxygen. A visible light absorbing substituted anthraquinone is synthesized, and nanosecond transient absorption spectroscopy is used to monitor the intermediates involved in the initiation mechanism. Photoproduct analysis indicates formation of methyl radicals as a result of DMSO oxidation. Furthermore, we show that the solvent outcompetes the chain transfer agent for interacting with the excited-state anthraquinone. These observations have a broad impact on photoinduced polymerizations performed in DMSO as many photocatalysts are strong oxidants in the excited state and are capable of reacting with the solvent. Therefore, the role of the solvent needs to be more carefully considered when proposing mechanisms for photoinduced polymerizations in DMSO.