{"title":"Photodimerization of dibenz[b,f] azepine derivatives and their reaction intermediates","authors":"Kazuo Ashikaga, Shinzaburo Ito, Masahide Yamamoto, Yasunori Nishijima","doi":"10.1016/0047-2670(87)87027-2","DOIUrl":null,"url":null,"abstract":"<div><p>It is clearly demonstrated that the photodimerization of 5-acyl dibenz[<em>b,f</em>]azepine (DBA) derivatives occurs via excited triplet intermediates. The excited triplet state of 5-acyl DBA derivatives is barely formed on direct excitation, but is formed efficiently by triplet—triplet (T—T) energy transfer from a triplet sensitizer. Benzophenone-sensitized photoexcitation gave a unique reaction product, the <em>anti</em>-cyclobutane dimer of DBA. Under the sensitized conditions, the quantum yield for the photodimerization was estimated to be 0.15 at 25°C ([DBA]=2.0×10<sup>−3</sup> mol l<sup>−1</sup>). The triplet intermediate of this reaction was detected by nanosecond laser photolysis and the kinetic parameters of the triplet species were determined.</p></div>","PeriodicalId":16771,"journal":{"name":"Journal of Photochemistry","volume":"38 ","pages":"Pages 321-329"},"PeriodicalIF":0.0000,"publicationDate":"1987-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/0047-2670(87)87027-2","citationCount":"4","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Photochemistry","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/0047267087870272","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 4
Abstract
It is clearly demonstrated that the photodimerization of 5-acyl dibenz[b,f]azepine (DBA) derivatives occurs via excited triplet intermediates. The excited triplet state of 5-acyl DBA derivatives is barely formed on direct excitation, but is formed efficiently by triplet—triplet (T—T) energy transfer from a triplet sensitizer. Benzophenone-sensitized photoexcitation gave a unique reaction product, the anti-cyclobutane dimer of DBA. Under the sensitized conditions, the quantum yield for the photodimerization was estimated to be 0.15 at 25°C ([DBA]=2.0×10−3 mol l−1). The triplet intermediate of this reaction was detected by nanosecond laser photolysis and the kinetic parameters of the triplet species were determined.
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