Color-Coding Visible Light Polymerizations To Elucidate the Activation of Trithiocarbonates Using Eosin Y

We report mechanistic investigations into aqueous visible-light reversible addition–fragmentation chain transfer (RAFT) polymerizations of acrylamides using eosin Y as a photoinduced electron-transfer (PET) catalyst. The photoinduced polymerization was found to be dependent upon the irradiation wavelength and reagents, where either reduction or oxidation of the PET catalyst leads to inherently different initiation and reversible-termination steps. Using blue light, multiple mechanisms of initiation are observed, depending on the presence or absence of a sacrificial reducing agent. Using green light, both an oxidative and a reductive PET initiation mechanism can be pursued. Investigations into the role of PET catalyst, wavelength, and reducing agent demonstrated that precise polymers with predictable molecular weights are best realized under an oxidative PET-RAFT mechanism. Therefore, this study provides fundamental insight into visible-light RAFT photopolymerizations and the role of eosin Y as a photoredox catalyst.