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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE

Formation and Direct Detection of Non-Conjugated Triplet 1,2-Biradical from β,γ-Vinylarylketone

H. Dushanee M. Sriyarathne A , Kosala R. S. Thenna-Hewa A , Tianeka Scott A and Anna D. Gudmundsdottir A B
+ Author Affiliations
- Author Affiliations

A Department of Chemistry, University of Cincinnati, Cincinnati, OH 45221, USA.

B Corresponding author. Email: anna.gudmundsdottir@uc.edu

Australian Journal of Chemistry 68(11) 1707-1714 https://doi.org/10.1071/CH15401
Submitted: 4 July 2015  Accepted: 1 September 2015   Published: 9 October 2015

Abstract

Laser flash photolysis of 2-methyl-1-phenylbut-3-en-1-one (1) conducted at irradiation wavelengths of 266 and 308 nm results in the formation of triplet 1,2-biradical 2 that has λmax at 370 and 480 nm. Biradical 2 is formed with a rate constant of 1.1 × 107 s–1 and decays with a rate constant of 2.3 × 105 s–1. Isoprene-quenching studies support the notion that biradical 2 is formed by energy transfer from the triplet-excited state of the ketone chromophore of 1. Density functional theory calculations were used to verify the characterization of triplet biradical 2 and validate the mechanism for its formation. Thus, it has been demonstrated that intramolecular sensitization of simple alkenes can be used to form triplet 1,2-biradicals with the two radical centres localized on the adjacent carbon atoms.


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