UV-Induced Hydrogen-Atom-Transfer Processes in 3-Thio-1,2,4-triazole Isolated in Ar and H<sub>2</sub> Low-Temperature Matrixes

Hanna Rostkowska; Leszek Lapinski; Maciej J. Nowak

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UV-Induced Hydrogen-Atom-Transfer Processes in 3-Thio-1,2,4-triazole Isolated in Ar and H₂ Low-Temperature Matrixes

机译：在Ar和H _{2 低温矩阵中分离的3-Thio-1,2,4-三唑中的紫外诱导的氢原子转移方法}

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The UV-induced thione → thiol phototautomeric reaction has been studied for monomeric 3-thio-1,2,4-triazole (3-ST) isolated in low-temperature Ar and n-H₂ (normal hydrogen) matrixes. Prior to any UV irradiation, monomers of 3-ST isolated in solid Ar or solid n-H₂ adopted mainly the most stable thione tautomeric form, as revealed by the IR spectra. Upon UV (λ > 275 nm) irradiation of 3-ST isolated in Ar matrixes, the IR bands due to this thione form decreased, while a set of initially weak bands increased in intensity. Growing bands indicated generation of a photoproduct, which was identified as the thiol tautomer with labile hydrogen atoms attached to sulfur and N(2) atoms. The UV-induced spectral changes allowed also identification of another minor thiol tautomer of 3-ST, which was present in the matrix prior to any irradiation and did not change its population upon exposure to UV light. The identification of the observed isomeric forms was supported by comparison of their separated experimental IR spectra with the spectra theoretically predicted for the various structures of 3-ST. The thione → thiol phototautomerization that was the main UV-induced process observed for 3-ST in Ar matrixes did not occur for monomers of the compound trapped in solid n-H₂.]]>

机译：<！[CDATA [

的UV诱导的硫酮→硫醇phototautomeric反应已经研究了单体3-硫代-1,2,4-三唑（ 3-ST ）分离在低温的Ar和NH <子> 2 （正常氢）矩阵。前的任何UV照射， 3-ST的单体分离出固体Ar或固体的N-H <子> 2 主要采取了最稳定的硫酮互变异构形式，如发现由IR光谱。当的 3-ST <的UV（λ> 275纳米）照射/ b>的分离，在Ar矩阵中，IR谱带由于该硫酮形式下降，而一组最初弱带的强度增加。生长条带指示的光化产物，将其鉴定为与附接到硫和N（2）原子不稳定的氢原子的巯基互变异构体的产生。也允许识别另一个次要的 3-ST的硫醇互变异构体的紫外线引起的光谱变化的，这是存在于任何照射之前的矩阵，且在暴露于UV光并没有改变它的人口。所观察到的异构体形式的识别是通过用理论上预测的 3-ST 的各种结构的光谱分离他们的实验红外光谱的比较的支持。硫酮→硫醇phototautomerization这是主要的UV诱导的过程观察到的 3-ST 在Ar中矩阵用于捕获在固体nH的<子> 2 的化合物的单体并没有出现。] ]> 展开▼

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2017年第37期|共10页

作者
Hanna Rostkowska; Leszek Lapinski; Maciej J. Nowak;
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Institute of Physics Polish Academy of Sciences Al. Lotnikow 32/46 02-668 Warsaw Poland;

Institute of Physics Polish Academy of Sciences Al. Lotnikow 32/46 02-668 Warsaw Poland;

Institute of Physics Polish Academy of Sciences Al. Lotnikow 32/46 02-668 Warsaw Poland;

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中图分类物理化学（理论化学）、化学物理学;

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UV-Induced Hydrogen-Atom-Transfer Processes in 3-Thio-1,2,4-triazole Isolated in Ar and H2 Low-Temperature Matrixes

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UV-Induced Hydrogen-Atom-Transfer Processes in 3-Thio-1,2,4-triazole Isolated in Ar and H₂ Low-Temperature Matrixes