Emily J Rabe, Kathryn L Corp, A. Sobolewski
Sep 28, 2018
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0
Influential Citations
41
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Journal
The journal of physical chemistry letters
Abstract
To gain mechanistic understanding of heptazine-based photochemistry, we synthesized and studied 2,5,8-tris(4-methoxyphenyl)-1,3,4,6,7,9,9b-heptaazaphenalene (TAHz), a model molecular photocatalyst chemically related to carbon nitride. On the basis of time-resolved photoluminescence (TR-PL) spectroscopy, we kinetically reveal a new feature that emerges in aqueous dispersions of TAHz. Using global target analysis, we spectrally and kinetically resolve the new emission feature to be blue shifted from the steady-state luminescence, and observe a fast decay component exhibiting a kinetic isotope effect (KIE) of 2.9 in H2O versus D2O, not observed in the steady-state PL. From ab initio electronic-structure calculations, we attribute this new PL peak to the fluorescence of an upper excited state of mixed nπ*/ππ* character. In water, the KIE suggests the excited state is quenched by proton-coupled electron transfer, liberating hydroxyl radicals that we detect using terephthalic acid. Our findings are consistent with recent theoretical predictions that heptazine-based photocatalysts can participate in proton-coupled electron transfer with H2O.