Under different solvents excited-state intramolecular proton transfer mechanism and solvatochromic effect of 2-(2-hydroxyphenyl) benzothiazole molecule
Under different solvents excited-state intramolecular proton transfer mechanism and solvatochromic effect of 2-(2-hydroxyphenyl) benzothiazole molecule
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不同溶剂下2-(2-羟基苯基)苯并噻唑分子激发态分子内质子转移机制及溶剂化变色效应
DOI：
10.1016/j.jlumin.2018.10.077
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发表时间：
2019-02
影响因子：
3.6
通讯作者：
Yongqing Li（李永庆）
中科院分区：
文献类型：
--
作者：
Yunfan Yang;Yunpeng Chen;Yu Zhao;Wei Shi;Fengcai Ma;Yongqing Li（李永庆）
在实验中合成了2-（2-羟基苯基）苯并噻唑分子（Xu等人，2017），在溶剂环境下观察到分子光物理现象，而该实验工作未能定性地揭示溶剂环境对光物理和光化学性质的影响。本研究首次采用含时密度泛函理论方法对激发态分子内质子转移和溶剂化变色效应的机理进行了深入的研究。计算得到的吸收光谱和发射光谱峰值与实验观察到的相对值非常吻合。在光激发过程中，描绘并分析了不同溶剂中的前线分子轨道和电荷转移激发度，揭示了溶剂化变色效应对光谱性质的影响。计算了不同溶剂中HBT-H、异构体HBT-T和阴离子HBT-A的最佳结构，通过比较氢键键参数和相应的红外振动频率，得到了不同溶剂下分子内氢键强度的大小顺序为PhMe > CH_3Cl> CH_2Cl_2> ACN > DMF。更重要的是，计算的施体和受体原子的Hirshfeld电荷基本上解释了溶剂极性对激发态分子内氢键强度的影响。由于氢键相互作用为质子转移反应提供了驱动力，通过计算反应活化能，进一步解释了溶剂极性对激发态分子内质子转移反应机理的影响。
2-(2-Hydroxyphenyl) benzothiazole molecule was synthesized in experiment (Xu et al., 2017), under solvent environments molecular photophysical phenomena were observed, while this experimental work failed to qualitatively unveil the effect of solvent environments on photophysical and photochemical properties. For the first time the mechanism of excited-state intramolecular proton transfer and solvatochromic effect were in depth investigated based on time-dependent density functional theory methods in this research. Calculated absorption and emission spectra peaks were very agreement with the relative values that observed in experiment. Upon photo-excitation process the frontier molecular orbitals and charge-transfer excitation degree were portrayed and analyzed in different solvents, unraveling the solvatochromic effect on spectral properties. Optimal normal HBT-H, isomer HBT-T and anion HBT-A structures were calculated in different solvents, the decreasing order of intramolecular hydrogen bond strength (PhMe > CH3Cl > CH2Cl2> ACN > DMF) under different solvents were obtained by comparing the bond parameters of hydrogen bond and corresponding infrared vibrational frequencies. More importantly, calculated Hirshfeld charges of donor and acceptor atoms essentially explained the effect of solvent polarities on excited-state intramolecular hydrogen-bond intensity. Because hydrogen bond interaction offered driving force for proton transfer reactions, the effect of solvent polarities on excited state intramolecular proton transfer reaction mechanism was further explained by calculating reactive activation energies.
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DOI：
10.1002/chin.200029270
发表时间：
2000-07
期刊：
ChemInform
影响因子：
--
作者：
M. Irie
通讯作者：
M. Irie
影响因子：
2.8
作者：
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通讯作者：
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影响因子：
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作者：
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通讯作者：
D. Sicińska;D. Truhlar;P. Paneth
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影响因子：
4.6
作者：
Yang Y;Zhao J;Li Y
通讯作者：
Li Y
影响因子：
4
作者：
K. Sakai;Takeo Tsuzuki;Y. Itoh;M. Ichikawa;Y. Taniguchi
通讯作者：
K. Sakai;Takeo Tsuzuki;Y. Itoh;M. Ichikawa;Y. Taniguchi