One-Way photoisomerization of cis-stilbene via a cation radical chain mechanism

Frederick D Lewis*, James R. Petisce, Joe D. Oxman, Marshall J. Nepras

*Corresponding author for this work

Research output: Contribution to journalArticle

76 Scopus citations

Abstract

Quenching of singlet 9,10-dicyanoanthracene by cis- or trans-stilbene in acetonitrile solution leads to a steady-state mixture consisting of 98.8% trans- and 1.2% cis-stilbene. Quantum yields for isomerization of cis-stilbene increase with increasing stilbene concentration, solvent polarity, salt concentration, and decreasing light intensity. These effects are attributed to a cation radical chain process in which the cis-stilbene cation radical isomerizes to the more stable trans-stilbene cation radical, which undergoes electron hole transfer to neutral cis-stilbene in competition with back electron transfer to the dicyanoanthracene anion radical. One-electron oxidation of cis-stilbene substantially lowers the activation energy for isomerization. In the presence of oxygen, the cation radical isomerization mechanism is suppressed and photooxygenation of cis- and trans-stilbene occurs.

Original languageEnglish (US)
Pages (from-to)203-207
Number of pages5
JournalJournal of the American Chemical Society
Volume107
Issue number1
DOIs
StatePublished - Jan 1 1985

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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