Visible-Light-Initiated Free-Radical Polymerization by Homomolecular Triplet-Triplet Annihilation

Summary Polymerization reactions initiated by ultraviolet light are ubiquitous in scores of industrial applications but would markedly benefit from visible-light activation to overcome stability, energy consumption, light penetration, and sample geometry limitations. The current work leverages visible-light-driven homomolecular triplet-triplet annihilation (TTA) in zinc(II) meso-tetraphenylporphyrin (ZnTPP) to initiate facile free-radical polymerization in trimethylolpropane triacrylate (TMPTA) and methyl acrylate (MA) monomers through ultrafast electron transfer quenching. Selective Q-band (S1) excitation of ZnTPP in the green or yellow sensitizes TTA occurring between two 3ZnTPP∗ energized chromophores, ultimately generating the highly reducing S2 excited state on one ZnTPP molecule (Ered = −2.13 V versus saturated calomel electrode, SCE). Subsequently, this S2 state engages in electron transfer with TMPTA or MA, thereby initiating the radical polymerization process. Bimolecular electron transfer was confirmed through optically gated fluorescence upconversion. FT-IR and EPR spin-trapping experiments verified visible-light-initiated polymerization leading to the formation of well-defined macro- and microscopic objects.