The Paternò–Büchi reaction: importance of triplet states in the excited-state reaction pathway

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DOIResolve DOI: http://doi.org/10.1039/c2cp40819h
AuthorSearch for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for: ; Search for:
TypeArticle
Journal titlePhysical Chemistry Chemical Physics
ISSN1463-9076
1463-9084
Volume14
Issue24
Pages85728580
AbstractThe Paternò–Büchi (PB) reaction between an excited carbonyl compound and an alkene has been widely studied, but so far little is known about the excited-state dynamics of the reaction. In this investigation, we used a compound in which a formyl and a vinyl group are attached to a [2.2]paracyclophane in order to obtain a model system in pre-reactive conformation for the PB reaction. We studied the excited-state dynamics of the isolated molecule in a molecular beam using femtosecond time-resolved photoelectron spectroscopy and ab initio calculations. The results show that inter-system crossing within two picoseconds competes efficiently with the reaction in the singlet manifold. Thus, the PB reaction in this model system takes place in the triplet state on a time scale of nanoseconds. This result stresses the importance of triplet states in the excited-state pathway of the PB reaction involving aromatic carbonyl compounds, even in situations in which the reacting moieties are in immediate vicinity.
Publication date
LanguageEnglish
AffiliationSecurity and Disruptive Technologies; Measurement Science and Standards; National Research Council Canada
Peer reviewedYes
NPARC number21268938
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Record identifier74ec4d5a-837d-4b6e-bece-1f8d54c1f049
Record created2013-11-27
Record modified2016-05-09
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