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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structure and Photoinduced Excited State Keto-Enol Tautomerization of 7-Hydroxyquinoline-(CH_3OH)_n Clusters
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Structure and Photoinduced Excited State Keto-Enol Tautomerization of 7-Hydroxyquinoline-(CH_3OH)_n Clusters

机译：7-羟基喹啉-（CH_3OH）_n团簇的结构和光诱导激发态酮-烯醇互变异构

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摘要

An investigation on the structures and the excited-state proton-transfer reaction has been carried out for size-selected 7-hydroxyquinoline(7HQ)-methanol hydrogen-bonded clusters in supersonic jets. The structures of the clusters were determined based on the analysis of the fluorescence-detected IR spectra in the OH stretching region and by density functional theory calculations. Two isomers were found to exist for 7HQ-(CH_3OH)_1. One has the form in which the OH group of 7HQ is hydrogen-bonded to the oxygen of CH_3OH, and the other has the form in which the OH group of CH_3OH is hydrogen-bonded tot he nitrogen of 7HQ. For 7HQ-(CH_3OH)_2 and -(CH_3OH)_3, their structures were determined to be "enol bridge" form, in which one end of a chain-formed methanol cluster is hydrogen-bonded to the OH group and the other to the nitrogen of 7HQ. Photoinduced excited-state proton-transfer reaction was investigated by measuring the dispersed fluorescence spectra for the clusters. Among them, a visible emission with a maximum at ～530 nm, which coincides with the tautomer emission of 7HQ generated in methanol solution, was observed for the enol bridge 7HQ-(CH_3OH)_3 and larger clusters. This result presents a direct evidence for the enol bridge form 7HQ-(CH_3OH)_3 to be a precursor for the proton-transfer reaction in solution.
机译：研究了超声速射流中尺寸选择的7-羟基喹啉（7HQ）-甲醇氢键团簇的结构和激发态质子转移反应。基于对OH拉伸区域中荧光检测的IR光谱的分析并通过密度泛函理论计算来确定簇的结构。发现存在7HQ-（CH_3OH）_1的两个异构体。一种具有其中7HQ的OH基氢键合到CH_3OH的氧上的形式，另一种具有其中CH_3OH的OH基氢键合到7HQ的氮上的形式。对于7HQ-（CH_3OH）_2和-（CH_3OH）_3，它们的结构被确定为“烯醇桥”形式，其中链状甲醇簇的一端与氢原子相连，另一端与氢原子相连。 7HQ的氮。通过测量团簇的分散荧光光谱，研究了光诱导的激发态质子转移反应。其中，对于烯醇桥7HQ-（CH_3OH）_3和较大的团簇，观察到最大在〜530 nm的可见光发射，这与在甲醇溶液中生成的7HQ的互变异构体发射一致。该结果提供了直接证据，证明7HQ-（CH_3OH）_3的烯醇桥为溶液中质子转移反应的前体。

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