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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Tautomer selective photochemistry in 1-(tetrazol-5-yl)ethanol
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Tautomer selective photochemistry in 1-(tetrazol-5-yl)ethanol

机译：1-（四唑-5-基）乙醇中的互变异构体选择性光化学

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摘要

A combined matrix isolation FTIR and theoretical DFT/B3LYP/6-311++G(d,p) study of the molecular structure and photochemistry of 1-(tetrazol-5-yl)ethanol [1-TE] was performed. The potential energy surface landscapes of the 1H and 2H tautomers of the compound were investigated and the theoretical results were used to help characterize the conformational mixture existing in equilibrium in the gas phase prior to deposition of the matrices, as well as the conformers trapped in the latter. In the gas phase, at room temperature, the compound exists as a mixture of 12 conformers (five of the 1H tautomer and seven of the 2H tautomer). Upon deposition of the compound in an argon matrix at 10 K, only three main forms survive, because the low barriers for conformational isomerization allow extensive conformational cooling during deposition. Deposition of the matrix at 30 K led to further simplification of the conformational mixture with only one conformer of each tautomer of 1-TE surviving. These conformers correspond to the most stable forms of each tautomer, which bear different types of intramolecular H-bonds: 1H-I has an NH···O hydrogen bond, whereas 2H-I has an OH···N hydrogen bond. Upon irradiating with UV light (λ > 200 nm), a matrix containing both 1H-I and 2H-I forms, an unprecedented tautomer selective photochemistry was observed, with the 2H tautomeric form undergoing unimolecular decomposition to azide + hydroxypropanenitrile and the 1H-tautomer being photostable.
机译：结合了基质分离FTIR和理论DFT / B3LYP / 6-311 ++ G（d，p）对1-（四唑-5-基）乙醇[1-TE]的分子结构和光化学进行了研究。研究了该化合物的1H和2H互变异构体的势能表面态势，并利用理论结果来帮助表征了在基质沉积之前气相中处于平衡状态的构象混合物，以及陷于其中的构象异构体。后者。在室温下的气相中，该化合物以12种构象异构体（5种1H互变异构体和7种2H互变异构体）的混合物形式存在。化合物在10 K的氩气基质中沉积后，只有三种主要形式得以保留，因为构象异构化的低阻隔层可在沉积过程中进行广泛的构象冷却。基质在30 K处的沉积导致构象混合物的进一步简化，其中每个1-TE互变异构体仅存在一个构象异构体。这些构象异构体对应于每个互变异构体的最稳定形式，它们带有不同类型的分子内H键：1H-1具有NH··O氢键，而2H-1具有OH··N氢键。在用紫外线（λ> 200 nm）照射时，同时包含1H-1和2H-1形式的基质，观察到空前的互变异构体选择性光化学，其中2H互变异构体形式发生单分子分解为叠氮化物+羟基丙腈和1H-互变异构体光稳定。

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