The facile generation of a tetramethyleneethane type radical cation and biradical utilizing a 3,4-di(alpha-styryl)furan and a photoinduced ET and back ET sequence.
Product analyses and nanosecond time-resolved spectroscopy on laser flash photolysis were studied for the photoinduced electron-transfer reaction of 3,4-di(alpha-styryl)furan (6a). A combination of these results, kinetic, density functional theoretical (DFT), and time-dependent DFT analyses enabled assignment of the absorption to the tetramethyleneethane (TME)-type radical cation (7a*+, lambda(max) = 392 nm) and the corresponding singlet biradical ((1)7a**, lambda(max) = 661 nm). These two intermediates were mechanistically linked to each other with a facile back electron-transfer reaction. The present studies provide a new method for the generation of aryl-substituted TME-type intermediates.
Ikeda
Teruyo
T
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Ikeda
Hiroshi
H
Takahashi
Yasutake
Y
Yamada
Masafumi
M
Mizuno
Kazuhiko
K
Tero-Kubota
Shozo
S
Yamauchi
Seigo
S
D000475:Alkenes / Q000737:chemistry* / Q000528:radiation effects; D002412:Cations / Q000737:chemistry / Q000528:radiation effects; D004583:Electrons; D004980:Ethane / Q000031:analogs & derivatives* / Q000737:chemistry / Q000528:radiation effects; D005609:Free Radicals / Q000737:chemistry / Q000528:radiation effects; D005663:Furans / Q000737:chemistry* / Q000528:radiation effects; D007834:Lasers; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008956:Models, Chemical; D015394:Molecular Structure; D010777:Photochemistry; D010782:Photolysis; D011789:Quantum Theory; D012015:Reference Standards
C527957:3,4-di(alpha-styryl)furan; D000475:Alkenes; D002412:Cations; D005609:Free Radicals; D005663:Furans; C527958:tetramethyleneethane; D004980:Ethane