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Early events in the photochemistry of 1,2,3-thiadiazole studied by ultrafast time-resolved UV - Vis and IR spectroscopies

机译:超快时间分辨的紫外-可见和红外光谱研究1,2,3-噻二唑光化学中的早期事件

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摘要

Photochemistry of 4-methyl-5-carboethoxy-1,2,3-thiadiazole (MCT) in solution was studied at room temperature using UV - vis and IR transient absorption spectroscopies (λ_(ex) = 266 nm). Three deactivation pathways are discussed: thiirene formation, thioketene generation, and the internal conversion by repopulating MCT in the ground state. Ultrafast techniques show a very fast rise (<0.4ps) of thiirene species in acetonitrile, possibly as a result of a rearrangement in the singlet excited state of MCT in concert with molecular nitrogen extrusion. The remarkable stability of thiirene in solution on a millisecond time scale is limited by the process of dimerization (thiirene - thiirene, thiirene - thioketene). NMR analysis permitted identification of stable photoproducts as 1,3-dithietane, 1,3-dithiole, and thiophene derivatives. (Figure presented)
机译:在室温下使用UV-vis和IR瞬态吸收光谱法(λ_(ex)= 266 nm)研究了溶液中的4-甲基-5-羰基乙氧基-1,2,3-噻二唑(MCT)的光化学。讨论了三种失活途径:噻吩的形成,硫代乙烯酮的产生以及通过在基态中重新填充MCT进行的内部转化。超快技术显示乙腈中噻吩类化合物的快速升高(<0.4ps),这可能是由于MCT的单线激发态与分子氮的挤出重排造成的。噻吩在毫秒级溶液中的显着稳定性受二聚作用(噻吩-噻吩,噻吩-硫代乙烯酮)的限制。 NMR分析可以鉴定稳定的光产物,如1,3-二硫杂环丁烷,1,3-二硫醇和噻吩衍生物。 (图示)

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