Excited state intramolecular proton transfer induced fluorescent change and decay pathway of salicylideneaniline
Excited state intramolecular proton transfer induced fluorescent change and decay pathway of salicylideneaniline
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水杨基苯胺激发态分子内质子转移诱导荧光变化和衰变途径
DOI：
10.1016/j.jlumin.2019.116736
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发表时间：
2019-12
影响因子：
3.6
通讯作者：
Liu Yufang
中科院分区：
文献类型：
--
作者：
Yang Yonggang;Zhai Hongsheng;Liu Yang;Jia Xueli;He Yuanyuan;Ma Qianfei;Jiang Kai;Liu Yufang
对水杨醛缩苯胺及其衍生物的荧光行为和非绝热动力学进行了理论研究。烯醇式的顺式酮在光激发后无任何能垒地跃迁到第一单激发态（S1），氯和羟基取代的衍生物也有类似的动力学过程。非绝热动力学结合光激发过程的结果表明，激发态质子在46 fs发生了分子内转移，几何结构和红外光谱的结果也证实了这一点。电势曲线扫描表明，Enol的质子转移反应前后的能量差（11.12 kcal/mol）大于Enol-CL的质子转移反应前后的能量差（8.97 kcal/mol），Enol的Stokes位移（257 nm）大于Enol-CL的Stokes位移（200 nm）和Enol-OH的Stokes位移（198 nm）。这一比较证实了氯和羟基的取代阻止了光激发后芳香性的降低以及基态（S 0）和S1态之间的能量差，从而诱导了较小的Stokes位移。烯醇与顺式酮的能垒（5.96 kcal/mol）和顺式酮与反式酮的能差（10.27 kcal/mol）很小，因此有烯醇（S 0）→质子转移顺式酮（S1）→荧光顺式酮（S 0）→烯醇（S 0）或顺式酮（S1）→反式酮（S1）→荧光反式酮（S 0）→烯醇（S 0）的衰变途径。
The fluorescent behaviors and nonadiabatic dynamics of salicylideneanilines and its two derivatives have been theoretical studied. The enol form transfers tocis-keto after photoexcitation to the first single (S1) excited state without any energy barrier, and the derivatives with substituent of chlorine and hydroxyl have similar dynamics progress. The excited state intramolecular proton transfer occurs in 46 fs by the results of nonadiabatic dynamics together with photoexcitation progress, which is also demonstrated by the results of geometric structure and infrared spectra. The potential curves scan indicates the energy difference before and after the proton transfer reaction of Enol (11.12 kcal/mol) is larger than that of Enol-CL (8.97 kcal/mol), and the Stokes shift of Enol (257 nm) is larger than that of Enol-CL (200 nm) and Enol-OH (198 nm). This comparison confirms the substitute of chlorine and hydroxyl hinder the decrease in aromaticity after photoexcitation and energy difference between the ground (S0) and the S1state, thereafter induce smaller Stokes shift. The energy barrier between Enol andCis-keto (5.96 kcal/mol) and energy difference betweenCis-keto andTrans-keto (10.27 kcal/mol) are so small that there is a decay pathway of Enol (S0)→proton transferredCis-keto (S1)→fluorescentCis-keto (S0)→Enol (S0) orCis-keto (S1) →Trans-keto (S1)→fluorescence ofTrans-keto (S0)→Enol (S0).
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影响因子：
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作者：
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