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Electronic absorption spectra and thermal stability of cis-trans isomers of diphenylbutadiene cation radicals

✍ Scribed by Stephan J. Hug; W.Atom Yee; David S. Kliger

Publisher: Elsevier Science
Year: 1990
Tongue: English
Weight: 483 KB
Volume: 168
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(90)85629-q

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✦ Synopsis

The cation radicals of the three cis-tram isomers of I ,4_diphenylbutadiene have been generated by pirradiation in a matrix at 77 K and in acetonitrile solution at room temperature by secondary electron transfer. The cation radicals exhibit two strong absorption bands, the more intense between 530 and 560 nm and another between 800 and 850 nm. The absorption bands of the cis,trans and the cis,cis isomers are red-shifted and have reduced oscillator strengths relative to those ofthe trans,trans isomer. In acetonitrile, cations with distinct absorption spectra were formed that do not thermally interconvert on a nanosecond time scale. Slow isomerization at room temperature does occur with an estimated lifetime of ;5 25 KS.

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