Photocycloaddition of 4,4-dimethylcyclohexenone to 1,1-diphenylethylene. Evidence for a triplet exciplex intermediate

Journal of the American Chemical Society

Volumn 118, Issue 36, 1996, Pages 8741-8742

  Caldwell, Richard A ^a   Hrncir, Duane C ^a   Muñoz Jr , Trinidad ^a   Unett, David J ^a  

^a UNIVERSITY OF TEXAS AT DALLAS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

PHENANTHRENE DERIVATIVE; POLYCYCLIC HYDROCARBON;

ARTICLE; DRUG SYNTHESIS; MOLECULAR DYNAMICS; NUCLEAR MAGNETIC RESONANCE; PHOTOCHEMISTRY; REACTION ANALYSIS;

EID: 0029818662     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9606891     Document Type: Article

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39. We considered that the 50 ns transient might be a 1,4-biradical. The head-to-tail biradical was investigated by 266 nm laser flash photolysis of 1. Its lifetime is 78 ns with an absorption spectrum similar to those of the DPE triplet and the new transient. Its lifetime is insensitive to the presence of isoprene up to a concentration of 0.3 M, consistent with its assignment as a biradical. Photolysis of 1 may produce the alternative head-to-head biradical. We have no quantitatitive information on the fragmentation of 1 under 266 nm photolysis but were aided by the fact that the head-to-head biradical is not spectroscopically observable. We considered further that the observed 50 ns decay might be a mixture of the 34 ns DPE triplet and a 78 ns biradical. Exhaustive multiple-component kinetic analyses lead us to reject this.
40. Δ refer to the fraction of oxygen quenching events leading to the production of singlet oxygen and the overall singlet oxygen quantum yield, respectively. For further information consult ref 44.
41. -1 s-1.
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