Journal
CHEM
Volume 6, Issue 11, Pages 3071-3085Publisher
CELL PRESS
DOI: 10.1016/j.chempr.2020.08.019
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Funding
- BioLEC, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0019370]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0011979]
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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 lever-ages 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 (S-1) excitation of ZnTPP in the green or yellow sensitizes TTA occurring between two (ZnTPP)-Zn-3* energized chromophores, ultimately generating the highly reducing S-2 excited state on one ZnTPP molecule (E-red = 2.13 V versus saturated calomel electrode, SCE). Subsequently, this S-2 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.
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