期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 122, 期 19, 页码 4601-4608出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.7b12339
关键词
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资金
- Department of Science and Technology (DST
- Nanomission Project), Government of India [SR/NM/NS-23/2016]
- DST
- Council of Scientific and Industrial Research, Government of India
- IISER-TVM
The met a effect in substituted aromatics plays a crucial role in their excited-state photophysical properties. Meta-substituted hydroxyarenes such as naphthols, stilbenols, and chromophoric constituents of green fluorescent proteins show unusual photoacidity and enhanced fluorescence lifetime and quantum yield when compared to their para-derivatives. Variation in the excited state features of the meta-derivatives when compared to the para-derivatives in stilbenols has been attributed to the enhanced torsional barrier for interconversion between the planar and the twisted perpendicular forms. Herein, we employed femtosecond time-resolved Raman spectroscopy to provide the direct structural evidence for the enhanced torsional barrier in meta-stilbenol. The Raman band profiles of the olefinic C=C stretch related to the torsional motion are found to decay with time constants of similar to 750 and similar to 13 ps in meta-stilbenol and para-stilbenol respectively, unraveling the structural evidence for the observed enhanced photoacidity originating from enhanced rates of excited-state proton transfer. Further, time-resolved fluorescence measurements are performed to elucidate the relaxation pathways of the excited states of the stilbenols.
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