Generation of Polyphenylene Radical Cations and Their Cosensitization Ability in the 9,10-Dicyanoanthracene-Sensitized Photochemical Chain Reactions of 1,2-Bis(4-methoxyphenyl)cyclopropane

• Published in: Journal of organic chemistry 1998-05, Vol.63 (10), p.3204-3212
• Main Authors: Tamai, Toshiyuki, Ichinose, Nobuyuki, Tanaka, Tomoko, Sasuga, Tsuneo, Hashida, Isao, Mizuno, Kazuhiko
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo971649y

Cosensitization effects of polyphenylene compounds (PP) such as biphenyl (BP), terphenyls (o-, m-, p-TP), and phenanthrene (Phen) in photoinduced electron-transfer reactions were examined. The 9,10-dicyanoanthracene (DCA)-sensitized cis−trans photoisomerization of 1,2-bis(4-methoxyphenyl)cyclopropane (CP), which proceeds in a chain reaction via free radical cation of CP (CP•+) as a chain carrier, was accelerated by adding PP, particularly by TP. A similar accelerating effect was observed in the DCA-sensitized photooxygenation of CP as another example. BP and TP were more stable under the oxygenation condition than phenanthrene and naphthalene, which also accelerate the photooxygenation CP. CP•+ is generated by the direct electron transfer from CP to the excited singlet state of DCA (1DCA*) and also by the secondary electron transfer from CP to PP•+, which is generated by the primary electron transfer from PP to 1DCA*. The laser flash photolysis study revealed that the quantum yield for the formation of free CP•+ in the direct electron transfer from CP to 1DCA* (ΦCP •+ ≈ 0.1) was smaller than that in the presence of PP. This is due to the high yield of free PP•+ generation by the primary electron transfer and the efficient secondary electron transfer from CP to PP•+. The secondary electron transfers were found to take place in nearly diffusion-controlled rates (0.9−1.5 × 1010 M-1 s-1). The high yield of PP•+ as free radical ions does not seem to be the sole factor of the cosensitization of PP for the DCA-sensitized photoreactions of CP. The ratio of the quantum yields of the photoreactions to that of the initial CP•+ formation (turnover) also increased by the addition of PP from 3 (isomerization) and 15 (oxygenation) to 32−90 for both reactions. The second-order rate constant for the decay of CP•+ in aerated acetonitrile was decreased by a factor of 0.5−0.8 by the addition of PP. We concluded that the cosensitization effect in the photoreaction involves a π-complex formation between CP•+ and PP assisting the chain reaction as well as initial CP•+ formation.