Organic Electron Donor–Acceptor Photoredox Catalysts: Enhanced Catalytic Efficiency toward Controlled Radical Polymerization

In this study, we designed and synthesized novel organic single electron donor-acceptor molecules containing a free base porphyrin and a thiocarbonylthio group. The porphyrin acts as a light-harvesting antenna and donates an excited electron upon light irradiation to the electron-accepting thiocarbonylthio group. The excited electronic state of the donor-acceptor generates a radical from the thiocarbonylthio compound to activate a living radical polymerization in the presence of monomers. Thus, these donor-acceptor systems play the roles of highly efficient photoredox catalysts and radical initiators. The presence of both donor and acceptor in a single molecule enhanced the electron transfer efficiency in comparison to the donor/acceptor mixture and consequently greatly increased polymerization rates of vinyl monomers under visible light irradiation. The polymerizations mediated by these electron donor-acceptor photoredox catalysts were investigated under green (λ_max = 530 nm, 0.7 mW/cm²) and red (λ_max = 635 nm, 0.7 mW/cm²) lights, which exhibited great control over molecular weights, molecular weight distributions, and end-group functionalities.