Direct observation of light-driven, concerted electron–proton transfer
Abstract
Here, the phenols 4-methylphenol, 4-methoxyphenol, and N-acetyl-tyrosine form hydrogen-bonded adducts with N-methyl-4, 4'-bipyridinium cation (MQ+) in aqueous solution as evidenced by the appearance of low-energy, low-absorptivity features in UV-visible spectra. They are assigned to the known examples of optically induced, concerted electron–proton transfer, photoEPT. The results of ultrafast transient absorption measurements on the assembly MeOPhO-H---MQ+ are consistent with concerted EPT by the instantaneous appearance of spectral features for MeOPhO·---H-MQ+ in the transient spectra at the first observation time of 0.1 ps. The transient decays to MeOPhO-H---MQ+ in 2.5 ps, accompanied by the appearance of oscillations in the decay traces with a period of ~1 ps, consistent with a vibrational coherence and relaxation from a higher υ(N-H) vibrational level or levels on the timescale for back EPT.
- Authors:
-
- Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290,
- Institute of Environmental Science, Shanxi University, Taiyuan, Shanxi, China 030006,
- Department of Chemistry, Memorial University of Newfoundland, St. John’s, NL, A1B 3X7, Canada
- Publication Date:
- Research Org.:
- Univ. of North Carolina at Chapel Hill, Chapel Hill, NC (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1326239
- Alternate Identifier(s):
- OSTI ID: 1464947
- Grant/Contract Number:
- SC0001011
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 40; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; light driven; electron; proton; transfer; photoEPT
Citation Formats
Gagliardi, Christopher J., Wang, Li, Dongare, Prateek, Brennaman, M. Kyle, Papanikolas, John M., Meyer, Thomas J., and Thompson, David W. Direct observation of light-driven, concerted electron–proton transfer. United States: N. p., 2016.
Web. doi:10.1073/pnas.1611496113.
Gagliardi, Christopher J., Wang, Li, Dongare, Prateek, Brennaman, M. Kyle, Papanikolas, John M., Meyer, Thomas J., & Thompson, David W. Direct observation of light-driven, concerted electron–proton transfer. United States. https://doi.org/10.1073/pnas.1611496113
Gagliardi, Christopher J., Wang, Li, Dongare, Prateek, Brennaman, M. Kyle, Papanikolas, John M., Meyer, Thomas J., and Thompson, David W. Thu .
"Direct observation of light-driven, concerted electron–proton transfer". United States. https://doi.org/10.1073/pnas.1611496113.
@article{osti_1326239,
title = {Direct observation of light-driven, concerted electron–proton transfer},
author = {Gagliardi, Christopher J. and Wang, Li and Dongare, Prateek and Brennaman, M. Kyle and Papanikolas, John M. and Meyer, Thomas J. and Thompson, David W.},
abstractNote = {Here, the phenols 4-methylphenol, 4-methoxyphenol, and N-acetyl-tyrosine form hydrogen-bonded adducts with N-methyl-4, 4'-bipyridinium cation (MQ+) in aqueous solution as evidenced by the appearance of low-energy, low-absorptivity features in UV-visible spectra. They are assigned to the known examples of optically induced, concerted electron–proton transfer, photoEPT. The results of ultrafast transient absorption measurements on the assembly MeOPhO-H---MQ+ are consistent with concerted EPT by the instantaneous appearance of spectral features for MeOPhO·---H-MQ+ in the transient spectra at the first observation time of 0.1 ps. The transient decays to MeOPhO-H---MQ+ in 2.5 ps, accompanied by the appearance of oscillations in the decay traces with a period of ~1 ps, consistent with a vibrational coherence and relaxation from a higher υ(N-H) vibrational level or levels on the timescale for back EPT.},
doi = {10.1073/pnas.1611496113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 40,
volume = 113,
place = {United States},
year = {Thu Sep 22 00:00:00 EDT 2016},
month = {Thu Sep 22 00:00:00 EDT 2016}
}
https://doi.org/10.1073/pnas.1611496113
Web of Science
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