Bulletin of the Chemical Society of Japan p. 3355 - 3362 (1991)
Update date:2022-08-02
Topics:
Karatsu, Takashi
Hiresaki, Tatsuro
Arai, Tatsuo
Sakuragi, Hirochika
Tokumaru, Katsumi
Wirz, Jakob
The effect of substitution of 3-chrysenyl group (Ar) on unsaturated double bonds in their triplet sensitized isomerization was investigated for Ar-CH=CH-R, R = tBu (BC) and Ph (SC) by means of stationary irradiations, laser flash photolyses, and MO calculations.Both olefins undergo mutual isomerization between their cis- and trans-isomers.However, BC has a unique triplet energy surface with two decay funnels at the planar trans (3t*) and twisted (3p*) conformations, which are in equilibrium with each other; 3t* undergoes either unimolecular decay to the ground-state trans isomer or triplet energy transfer to the cis isomer (quantum chain process) and 3p* decays to the ground state to give the cis and trans isomers.Tn <- T1 absorptions observed for BC and SC are mainly attributed to 3t* and 3p*, respectively, on the basis of semiempirical MO calculations.The populations at 3t* and 3p* are estimated.
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