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一个新的七元环吡咯-吡啶氢键分子激发态分子内质子转移的理论研究

Theoretical study on excited-state intramolecular proton transfer of a new seven-membered ring pyrrole-pyridine bond molecule containing hydrogen bonding
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摘要 运用含时密度泛函理论(TD-DFT)方法和以环己烷为溶剂的可极化连续模型(PCM),研究了2-[2-(1 H-pyrrol-2-yl)-cyclopent-1-enyl]-pyridine(7-HB)发生激发态分子内质子转移(ESIPT)的反应机制.结果表明,7-HB分子被光激发到Franck-Condon区域后,在第一光学亮态(S_1)上会发生一个超快的从Normal(N)式到Tautomer(T)式的质子转移反应,其反应的能垒仅有0.05eV.此外,在相同计算水平下,还研究了7-HB分子的吸收和发射光谱,所得结果与实验数据吻合得很好. Time-dependent density functional theory（TDDFT）approaching along with the polarizable continuum model（PCM）using cyclohexane as a solvent was used to explore the excited-state intramolecular proton transfer（ESIPT）reaction of 2-[2-（1 H-pyrrol-2-yl）-cyclopent-1-enyl]-pyridine（7-HB）.The result indicated that while the 7-HB molecule was photoexcited into the Franck-Condon region,it could undergo an ultrafast proton transfer reaction from the normal（N）to tautomer（T）forms in the optically bright first excited singlet state（S_1）,with a negligible barrier of 0.05 eV.In addition,the absorption and emission spectra of 7-HB were also calculated at the same theoretical level.It was found that our theoretical predictions were in good agreement with the available experimental findings.
作者 袁慧娟 郭续更
机构地区 河南大学化学化工学院
出处 《化学研究》 CAS 2016年第3期294-298,共5页 Chemical Research
基金 国家自然科学基金项目(21503069)
关键词 含时密度泛函理论 激发态分子内质子转移 七元环分子 氢键 TD-DFT excited-state intramolecular proton transfer seven-membered ring molecule hydrogen bonding
分类号 O641.3 [理学—物理化学]
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参考文献22

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化学研究
2016年 第3期

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