Highly Efficient Conformer-Specific Adiabatic Cis Trans Photoisomerization of cis-1-(2-Anthryl)-2-phenylethene in S1
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- 作者：Jack Saltiel ; Yuxin Zhang ; and Donald F. Sears ; Jr.
- 刊名：Journal of the American Chemical Society
- 出版年：1996
- 出版时间：March 27, 1996
- 年：1996
- 卷：118
- 期：12
- 页码：2811 - 2817
- 全文大小：293K
- 年卷期：v.118,no.12(March 27, 1996)
- ISSN：1520-5126
文摘
Emission from cis-1-(2-anthryl)-2-phenylethene,c-APE, in toluene consists primarily (up to 76%)offluorescence from adiabatically formed 1t-APEB*. In this respect, the behavior ofc-APE is analogous to that of thenaphthyl analogue, c-NPE. However, the conformerspecific adiabaticphotoisomerization,1c-APEB* 
f">1t-APEB*,is much more efficient in c-APE than in c-NPE(
f">44% vs f">2%) although the lifetime of1c-APEB* is 1000-foldlonger than the lifetime of 1c-NPEB*(4.5 ± 0.5 ns vs 4 ± 1 ps). Resolution of the spectra of1c-APE* and1t-APEB*was achieved by application of principal component analysis on a matrixof sets of fluorescence spectra measuredin the presence of Ar, air, and O2. The knownfluorescence spectrum of t-APEB and the knownStern-Volmerconstant for O2 quenching of the fluorescence oft-APEB serve as the constraints for thisresolution. Sequentialquenching by O2 of1c-APEB* and1t-APEB* is reflected in a quadraticStern-Volmer plot for the latter.
f">1t-APEB*,is much more efficient in c-APE than in c-NPE(f">44% vs f">2%) although the lifetime of1c-APEB* is 1000-foldlonger than the lifetime of 1c-NPEB*(4.5 ± 0.5 ns vs 4 ± 1 ps). Resolution of the spectra of1c-APE* and1t-APEB*was achieved by application of principal component analysis on a matrixof sets of fluorescence spectra measuredin the presence of Ar, air, and O2. The knownfluorescence spectrum of t-APEB and the knownStern-Volmerconstant for O2 quenching of the fluorescence oft-APEB serve as the constraints for thisresolution. Sequentialquenching by O2 of1c-APEB* and1t-APEB* is reflected in a quadraticStern-Volmer plot for the latter.