- Steady-State and Laser Flash Photolysis Studies of Bridgehead-Substituted Dibenzobarrelenes.
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The photochemistry of bridgehead-substituted dibenzobarrelenes 1a-h (Scheme I) has been investigated by steady-state photolysis, product analysis, and time-resolved laser flash photolysis. 4b-Substituted dibenzosemibullvalenes 8b,c,f,g are formed as major photoproducts from dibenzobarrelenes 1b,c,f,g,bearing acetoxy, formyl, ethyl, and methoxy 9 -bridgehead substituents, whereas 8b-substituted dibenzosemibullvalenes (or products derived from them) (7 and 6e) are formed from 9-hydroxy- and 9-cyano-substituted dibenzobarrelenes 1a,e.Laser flash photolysis gives rise totransient phenomena attributable to the triplets of dibenzobarrelenes (ΦT = 0.2-0.7 in benzene).These are characterized by broad and diffuse absorption spectra, short lifetimes (0.07-11 μs), and varying degrees of quenchability by azulene, ferrocene, β-carotene, and p-methoxyphenol.The rate constants for triplet quenching by the latter quenchers as well as oxygen and di-tert-butylnitroxy radicals are presented.
- Murty, Bulusu A. R. C.,Pratapan, Sreedharan,Kumar, Challa V.,Das, Paritosh K.,George, Manapurathu V.
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p. 2533 - 2538
(2007/10/02)
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