Crystalline-state Z,E-photoisomerization of a series of (Z,E,Z)-1,6-diphenylhexa-1,3,5-triene 4,4'-dicarboxylic acid dialkyl esters. Chain length effects on the crystal structure and photoreactivity.
Crystalline-state Z,E-photoisomerization of a series of (Z,E,Z)-1,6-diphenylhexa-1,3,5-triene 4,4'-dicarboxylic acid dialkyl esters. Chain length effects on the crystal structure and photoreactivity.
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一系列 (Z,E,Z)-1,6-二苯基六-1,3,5-三烯 4,4-二羧酸二烷基酯的晶态 Z,E-光异构化。
DOI：
10.1021/jo051137g
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发表时间：
2005
期刊：
影响因子：
--
通讯作者：
M. Goto
中科院分区：
文献类型：
--
作者：
Y. Sonoda;Y. Kawanishi;S. Tsuzuki;M. Goto
一系列（Z，E，Z）-1,6-二苯基六甲酸-1,3,5-三烯4,4'-二羧酸二烷基(R)酯的结晶态Z，E-光异构化[(Z，E，Z)-1a, R = Me；（Z，E，Z）-1b, R = Et；（Z，E，Z）-1c, R = n-Pr；（Z，E，Z）-1d, R = n-Bu]。所有的Z，E，Z异构体都单向异构为相应的E，E，E异构体。随着烷基链长度的增加，反应效率显著提高。对（Z，E，Z）-1a-d的单晶x射线分析表明，随着链长的增加，晶体的烷基链部分变大。烷基链的构象柔韧性使得晶格中的三烯几何结构发生较大变化，从而增强了晶体状态下的光反应性。
[reaction: see text] Crystalline-state Z,E-photoisomerization of a series of (Z,E,Z)-1,6-diphenylhexa-1,3,5-triene 4,4'-dicarboxylic acid dialkyl (R) esters [(Z,E,Z)-1a, R = Me; (Z,E,Z)-1b, R = Et; (Z,E,Z)-1c, R = n-Pr; (Z,E,Z)-1d, R = n-Bu] was investigated. All Z,E,Z isomers underwent one-way isomerization to the corresponding E,E,E isomers. The reaction efficiency was strongly enhanced as the length of the alkyl chain increased. Single-crystal X-ray analyses of (Z,E,Z)-1a-d showed that the alkyl chain part of the crystals became larger as the chain length increased. The conformational flexibility of the alkyl chains made the large change in the triene geometry in the lattice possible, leading to the enhancement of the photoreactivity in the crystalline state.