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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
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-09-12 00:00:00 , DOI: 10.1021/acs.jpca.7b05621 Hanna Rostkowska 1 , Leszek Lapinski 1 , Maciej J. Nowak 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-09-12 00:00:00 , DOI: 10.1021/acs.jpca.7b05621 Hanna Rostkowska 1 , Leszek Lapinski 1 , Maciej J. Nowak 1
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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.
中文翻译：
在Ar和H 2低温基质中分离的3-硫1,2-，4-三唑中的紫外线诱导的氢原子转移过程
对于在低温Ar和nH 2（正氢）基质中分离的单体3-硫代1,2,4-三唑（3-ST），已经研究了UV诱导的thione→硫醇光互变异构反应。在任何紫外线照射之前，如红外光谱所示，在固态Ar或固态nH 2中分离出的3-ST单体主要采用最稳定的硫酮互变异构形式。在3-ST的UV（λ> 275 nm）照射下在Ar基质中分离得到的硫带形式，IR谱带减少，而一组最初的弱谱带的强度增加。增长的条带表明产生了光产物，该产物被鉴定为硫醇互变异构体，其不稳定的氢原子与硫和N（2）原子相连。紫外线引起的光谱变化还可以鉴定出另一种较小的3-ST硫醇互变异构体，该物质在任何辐照之前都存在于基质中，并且在暴露于紫外线下不会改变其种群。观察到的异构体形式的鉴定通过将其分离的实验IR光谱与3-ST各种结构的理论预测光谱进行比较来支持。对于Ar基质中3-ST所观察到的主要UV诱导过程，硫酮→硫醇光互变异构对于固体nH 2中捕获的化合物的单体而言并未发生。
更新日期：2017-09-12
中文翻译：
在Ar和H 2低温基质中分离的3-硫1,2-，4-三唑中的紫外线诱导的氢原子转移过程
对于在低温Ar和nH 2（正氢）基质中分离的单体3-硫代1,2,4-三唑（3-ST），已经研究了UV诱导的thione→硫醇光互变异构反应。在任何紫外线照射之前，如红外光谱所示，在固态Ar或固态nH 2中分离出的3-ST单体主要采用最稳定的硫酮互变异构形式。在3-ST的UV（λ> 275 nm）照射下在Ar基质中分离得到的硫带形式，IR谱带减少，而一组最初的弱谱带的强度增加。增长的条带表明产生了光产物，该产物被鉴定为硫醇互变异构体，其不稳定的氢原子与硫和N（2）原子相连。紫外线引起的光谱变化还可以鉴定出另一种较小的3-ST硫醇互变异构体，该物质在任何辐照之前都存在于基质中，并且在暴露于紫外线下不会改变其种群。观察到的异构体形式的鉴定通过将其分离的实验IR光谱与3-ST各种结构的理论预测光谱进行比较来支持。对于Ar基质中3-ST所观察到的主要UV诱导过程，硫酮→硫醇光互变异构对于固体nH 2中捕获的化合物的单体而言并未发生。
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