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Reaction Mechanism of Photodeamination Induced by Excited-State Intramolecular Proton Transfer of the Anthrol Molecule
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-06-04 00:00:00 , DOI: 10.1021/acs.jpca.8b04150
Yunfan Yang 1 , Yong Ding 1 , Yu Zhao 1 , Fengcai Ma 1 , Yongqing Li 1
Affiliation  

The photodeamination reaction of the anthrol molecule generating the high-activity quinone methide intermediate has been investigated ( J. Org. Chem. 2017, 82, 6006−6021), though lacking careful explanation for its reaction mechanism. In our research, the mechanism of the anthrol molecule photodeamination induced by excited-state intramolecular proton transfer was reported for the first time. Absorption and emission spectra calculated for the work presented here agreed well with experimental results. To propose a molecular-level explanation of the photodeamination reaction, we calculated bond parameters, corresponding infrared vibrational frequencies, Mayer bond orders, and visualized frontier molecular orbitals of different molecules, and the hydrogen bond strengthening behavior in excited states was confirmed, enhancing the excited state intramolecular proton transfer of the anthrol molecule. Moreover, we concluded that photoisomerization weakened the bond strength between nitrogen and carbon atoms, which promoted the photodeamination reaction. Finally, for visually and quantificationally revealing the photodeamination mechanism, we have established the three-dimensional potential energy surfaces for the deamination reaction in different electronic states and calculated the corresponding reaction Gibbs free energies, it can be confirmed that the photodeamination reaction of the anthrol molecule must be induced by a proton transfer reaction in the excited state.

中文翻译:

兴奋态分子内质子转移到蒽酚上引起的光脱氨反应机理

的蒽分子生成高活性的醌甲基化物中间体的反应photodeamination已经研究了(有机化学杂志。 2017年82(6006-6021),尽管对其反应机理缺乏详尽的解释。在我们的研究中,首次报道了激发态分子内质子转移引起的蒽酚光脱氨的机理。为此处介绍的工作计算的吸收光谱和发射光谱与实验结果非常吻合。为了提出光脱氨反应的分子水平解释,我们计算了键参数,相应的红外振动频率,Mayer键阶数以及不同分子的可视化前沿分子轨道,并确认了激发态的氢键强化行为,从而增强了激发态。状态表示蒽酚分子内质子转移。此外,我们得出的结论是,光异构化削弱了氮和碳原子之间的键合强度,促进了光脱氨反应。最后,为了可视化和定量地揭示光脱氨机理,我们建立了在不同电子状态下的脱氨反应的三维势能面,并计算了相应的反应吉布斯自由能,可以证实蒽酚分子的光脱氨反应。必须由处于激发态的质子转移反应诱导。
更新日期:2018-06-04
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