HIGHLY SELECTIVE CIS-TRANS PHOTOISOMERIZATION OF 1-PYRENYLETHYLENES - RELATIONS BETWEEN THE MODES OF ISOMERIZATION AND POTENTIAL-ENERGY SURFACES

被引：37

作者：

OKAMOTO, H ^{[1
]}

ARAI, T ^{[1
]}

SAKURAGI, H ^{[1
]}

TOKUMARU, K ^{[1
]}

机构：

[1] UNIV TSUKUBA, DEPT CHEM, SAKURA, IBARAKI 305, JAPAN

来源：

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN | 1990年 / 63卷 / 10期

关键词：

D O I：

10.1246/bcsj.63.2881

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Among 1-pyrenylethylenes with an alkyl (t-butyl) or an aryl (phenyl) group on the ß ethylenic carbon, 1-(3,3-dimethyl-1-butenyl)pyrene (BP) undergoes cis-to-trans one-way isomerization on benzil sensitization, whereas 1-styrylpyrene (SP) undergoes mutual isomerization between the cis and trans isomers to afford an extremely high photostationary state composition (98%) of the trans isomer. Transient spectroscopy and measurements of the isomerization quantum yields revealed that the trans triplet state is the most stable and populated conformation on the triplet energy surface for both BP and SP; however, a higher degree of stabilization of the trans conformation for BP than for SP compared to the perpendicularly twisted conformation makes BP and SP one-way and two-way isomerizing, respectively. © 1990 The Chemical Society of Japan.

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页码：2881 / 2890

页数：10

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