期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 113, 期 40, 页码 11106-11109出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1611496113
关键词
light driven; electron; proton; transfer; photoEPT
资金
- National Science Foundation [CHE-1362481]
- Natural Sciences and Engineering Research Council of Canada
- Memorial University
- US Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001011]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1362481] Funding Source: National Science Foundation
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 center dot-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 similar to 1 ps, consistent with a vibrational coherence and relaxation from a higher nu(N-H) vibrational level or levels on the timescale for back EPT.
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