Intrinsic rate of electron transfer in the diffusional quenching of trans-stilbene S1 by fumaronitrile
Intrinsic rate of electron transfer in the diffusional quenching of trans-stilbene S1 by fumaronitrile
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富马腈扩散猝灭反式二苯乙烯 S1 时电子转移的固有速率
DOI：
10.1021/j100339a041
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发表时间：
1989
期刊：
影响因子：
--
通讯作者：
K. Peters
中科院分区：
文献类型：
--
作者：
S. Angel;K. Peters
特别令人感兴趣的是，由于该系统已被用作各种理论模型的测试，用于将溶剂摩擦耦合到异构化的大幅度运动。早在1902年，人们就报道了二苯乙烯的光二聚反应生成四苯基环丁烷。1968年，Chapman观察到反式二苯乙烯与四甲基乙烯的光环加成反应的量子产率与温度成反比。在反式二苯乙烯与2，5-二甲基-2，4-己二烯的光环加成反应中观察到微弱的激基络合物发射。为了解释这些观察，提出了激基复合体的干预。69刘易斯和他的同事们已经彻底研究了激基复合体在二苯乙烯光化学中的作用。从这些和许多其他研究中，我们发现二苯乙烯的光环加成反应发生在激基复合体中。最近，我们报道了一系列关于反式二苯乙烯在富马腈存在下的光化学的研究。8-10该体系在非极性溶剂中表现出很强的激基缔合物发射，但不发生光环加成反应。二苯乙烯间电荷转移带的355 nm辐射
of particular interest, as this system has been used as a test of various theoretical models for the coupling of the solvent friction to the large-amplitude motion of the isomerization.’-“ trans-Stilbene also displays a very rich photochemistry. As early as 1902, the photodimerization of stilbene to give tetraphenylcyclobutane was rep~rted.~ In 1968, Chapman observed6 an inverse temperature dependence upon the quantum yield for the photocycloaddition of trans-stilbene with tetramethylethylene. Weak exciplex emission was observed in the photocycloaddition of trans-stilbene with 2,5-dimethyl-2,4- hexadiene.’ To account for these observations, the intervention of an exciplex was proposed.69’ The role of the exciplex in stilbene’s photochemistry has been thoroughly addressed by Lewis and co-workers.’ From these and numerous other studies, it is found that photocycloaddition reactions of stilbene occur within the exciplex. Recently we reported a series of investigations into the pho- tochemistry of trans-stilbene in the presence of fumaronitrile.8-10 This system displays strong exciplex emission in nonpolar solvents but does not undergo a photocycloaddition reaction. The 355-nm irradiation of the charge-transfer band formed between stilbene