Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 122, Issue 8, Pages 2379-2388Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.7b12542
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Funding
- U.S. Department of Energy, Office of Basic Sciences, Division of Chemical Sciences, Geosciences [DE-SC0001780, DE-SC0008640, DE-SC0012704]
- U.S. Department of Energy (DOE) [DE-SC0001780, DE-SC0008640] Funding Source: U.S. Department of Energy (DOE)
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Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr. Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc. 139, 2017, 14568]. Herein, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution. The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.
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