Pressure effects on the photocycloaddition of 2-adamantanone with fumaronitrile

Nicholas J. Turro*, Wen-Sheng Chung, Masami Okamoto

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

The photochemical [2+2] cycloaddition of 2-adamantanone (AD) with trans-dicyanoethylene (t-DCE) was studied in acetonitrile as a function of pressure, and the activation volumes for both singlet and triplet reactions were determined. The competing reactions between excited singlet and triplet states of AD were found to be pressure dependent. At high pressure, the intersystem crossing rate, kst, from singlet to triplet increased, and as a result the singlet lifetime of AD was shortened and the triplet reaction which leads to cis-trans isomerization of the starting olefin became favored as pressure was increased. The Stern-Volmer slopes were found to correlate linearly with solvent viscosity; however, the triplet reaction (kqt/kt) correlated linearly only with the solvent dielectric constant.

Original languageEnglish
Pages (from-to)17-27
Number of pages11
JournalJournal of Photochemistry and Photobiology, A: Chemistry
Volume45
Issue number1
DOIs
StatePublished - 1 Jan 1988

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