Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 123, Issue 49, Pages 29580-29588Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.9b08842
Keywords
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Funding
- Washington Research Foundation
- University of Washington Clean Energy Institute (CEI)
- National Science Foundation [ECC-1542101]
- Office of Naval Research Defense University Research Instrumentation Program [N00014-14-1-0757]
- University of Washington, Molecular Engineering & Sciences Institute, Clean Energy Institute
- National Institutes of Health
- US National Science Foundation (NSF) [1846480]
- Munich Centre for Advanced Photonics (MAP)
- Alexander von Humboldt Research Award
- Clean Energy Institute
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1846480] Funding Source: National Science Foundation
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To inform prospective design rules for controlling aza-arene photochemistry, we studied hydrogen-bonded complexes of 2,5,8-tris(4-methoxyphenyl)-1,3,4,6,7,9,9b-heptaazaphenalene (TAHz), a molecular photocatalyst chemically related to graphitic carbon nitride, with a variety of phenol derivatives. We have focused on excited state proton-coupled electron transfer (ES-PCET) reactions of heptazines because the excited state properties governing this process remain conceptually opaque compared to proton reduction reactions for these materials. We used ground-state absorption, time-resolved photoluminescence, and ab initio quantum chemical calculations to analyze TAHz reactivity toward a series of six para-substituted phenol derivatives. We determined association constants (K-A), excited-state quenching rate constants (k(Q)), kinetic isotope effects, and transition-state barriers (Delta E-double dagger). From this data, we provide a generalizable picture of hydrogen bond formation and excited state reactivity of heptazine-based materials with hydrogen-atom donating solvents. These results provide important insights into strategies to tune charge transfer state energies and increase ES-PCET rates.
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