The Facile Generation of a Tetramethyleneethane Type Radical Cation and Biradical Utilizing a 3,4-Di(-styryl)furan and a Photoinduce
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- 作者：Teruyo Ikeda ; Hiroshi Ikeda ; Yasutake Takahashi ; Masafumi Yamada ; Kazuhiko Mizuno ; Shozo Tero-Kubota ; Seigo Yamauchi
- 刊名：Journal of the American Chemical Society
- 出版年：2008
- 出版时间：February 27, 2008
- 年：2008
- 卷：130
- 期：8
- 页码：2466 - 2472
- 全文大小：151K
- 年卷期：v.130,no.8(February 27, 2008)
- ISSN：1520-5126
文摘
Product analyses and nanosecond time-resolved spectroscopy on laser flash photolysis werestudied for the photoinduced electron-transfer reaction of 3,4-di(
-styryl)furan (6a). A combination of theseresults, kinetic, density functional theoretical (DFT), and time-dependent DFT analyses enabled assignmentof the absorption to the tetramethyleneethane (TME)-type radical cation (7a
+, 
max = 392 nm) and thecorresponding singlet biradical (17a, max = 661 nm). These two intermediates were mechanistically linkedto each other with a facile back electron-transfer reaction. The present studies provide a new method forthe generation of aryl-substituted TME-type intermediates.
-styryl)furan (6a). A combination of theseresults, kinetic, density functional theoretical (DFT), and time-dependent DFT analyses enabled assignmentof the absorption to the tetramethyleneethane (TME)-type radical cation (7a+, max = 392 nm) and thecorresponding singlet biradical (17a, max = 661 nm). These two intermediates were mechanistically linkedto each other with a facile back electron-transfer reaction. The present studies provide a new method forthe generation of aryl-substituted TME-type intermediates.