Photoisomerization of cis-1,2-di(1-Methyl-2-naphthyl)ethene at 77 K in Glassy Media

被引:8
作者
Redwood, Christopher [1 ]
Kumar, V. K. Ratheesh [1 ]
Hutchinson, Stuart [1 ]
Mallory, Frank B. [2 ]
Mallory, Clelia W. [3 ]
Clark, Ronald J. [1 ]
Dmitrenko, Olga [4 ]
Saltiel, Jack [1 ]
机构
[1] Florida State Univ, Dept Chem & Biochem, Tallahassee, FL 32306 USA
[2] Bryn Mawr Coll, Dept Chem, Bryn Mawr, PA 19010 USA
[3] Univ Penn, Dept Chem, Philadelphia, PA 19104 USA
[4] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA
基金
美国国家科学基金会;
关键词
CIS-TRANS PHOTOISOMERIZATION; SINGULAR-VALUE DECOMPOSITION; HULA-TWIST; EXCITATION-ENERGIES; STILBENE; SPECTRA; BACTERIORHODOPSIN; PHOTOCHEMISTRY; MECHANISM; BOND;
D O I
10.1111/php.12367
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
cis-1,2-Di(1-methyl-2-naphthyl)ethene, c-1,1, undergoes photoisomerization in methylcyclohexane, isopentane and diethyl ether/isopentane/ethanol glasses at 77K. On 313nm excitation the fluorescence of c-1,1 is replaced by fluorescence from t-1,1. Singular value decomposition reveals that the spectral matrices behave as two component systems suggesting conversion of a stable c-1,1 conformer to a stable t-1,1 conformer. However, the fluorescence spectra are (exc) dependent. Analysis of global spectral matrices shows that c-1,1 is a mixture of two conformers, each of which gives one of four known t-1,1 conformers. The (exc) dependence of the c-1,1 fluorescence spectrum is barely discernible. Structure assignments to the resolved fluorescence spectra are based on the principle of least motion and on calculated geometries, energy differences and spectra of the conformers. The relative shift of the c-1,1 conformer spectra is consistent with the shift of the calculated absorption spectra. The calculated structure of the most stable conformer of c-1,1 agrees well with the X-ray crystal structure. Due to large deviations of the naphthyl groups from the ethenic plane in the conformers of both c- and t-1,1 isomers, minimal motion of these bulky substituents accomplishes cis trans interconversion by rotation about the central bond.
引用
收藏
页码:607 / 615
页数:9
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