Theoretical Investigation of the Reaction Mechanism of Photodeamination Induced by Excited-State Intramolecular Proton Transfer of Cresol Derivatives

doi:10.1021/acs.jpca.7b11571

	Theoretical Investigation of the Reaction Mechanism of Photodeamination Induced by Excited-State Intramolecular Proton Transfer of Cresol Derivatives
	Yang, Yunfan 1,2; Ma, Yanzhen 1; Zhao, Yu 1; Zhao, Yanliang 3; Li, Yongqing 1,2
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2018-02-01
卷号	122 期号:4 页码:1011-1018
ISSN号	1089-5639
DOI	10.1021/acs.jpca.7b11571
文献子类	Article
英文摘要	The novel photodeamination process of cresol derivatives 1 and 3 has been reported experimentally (j. Org. Chem. 2015, 80, 10817). However, a full theoretical interpretation of the mechanism is still lacking. In the present study, we aim to provide insight into the factors that promote the deamination reaction through density functional theory (DFT) and time dependent OFT methods. Calculated absorption and emission spectra arc in good agreement with the experimental results. Hydrogen-bond strengthening in the excited state has been verified by analyzing relevant bond parameters and vibrational frequencies as well as frontier molecular orbitals (FMOs), implying that hydrogen-bond interaction acts as the important parameter for the excited-state intramolecular proton-transfer (ESIPT) reaction. The proton-transfer and deamination reactions have been qualitatively analyzed through Gibbs free-energy reaction profiles in different electronic states. It can be concluded that the ESIPT and photodeamination reactions occur in the excited state. To further illustrate the photodeamination mechanism, the constructed 2D potential-energy surface indicates that the photodeamination reaction is infeasible without the ESIPT reaction. This work provides the first theoretical rationale for ESIPT-induced photodeamination occurring spontaneously because of protonation of a basic nitrogen atom.
WOS关键词	PHOTOINDUCED ELECTRON-TRANSFER ; DENSITY-FUNCTIONAL THEORY ; DNA-BASE PAIR ; TD-DFT ; QUINONE METHIDE ; ALCOHOLS ; PEROXYNITRITE ; GLUTATHIONE ; 7-AZAINDOLE ; FLUORENONE
WOS研究方向	Chemistry ; Physics
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000424316400018
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/168752]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
通讯作者	Li, Yongqing
作者单位	1.Liaoning Univ, Dept Phys, Shenyang 110036, Liaoning, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China 3.Ludong Univ, Sch Phys & Optoelect Engn, Yantai 264025, Peoples R China
推荐引用方式 GB/T 7714	Yang, Yunfan,Ma, Yanzhen,Zhao, Yu,et al. Theoretical Investigation of the Reaction Mechanism of Photodeamination Induced by Excited-State Intramolecular Proton Transfer of Cresol Derivatives[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2018,122(4):1011-1018.
APA	Yang, Yunfan,Ma, Yanzhen,Zhao, Yu,Zhao, Yanliang,&Li, Yongqing.(2018).Theoretical Investigation of the Reaction Mechanism of Photodeamination Induced by Excited-State Intramolecular Proton Transfer of Cresol Derivatives.JOURNAL OF PHYSICAL CHEMISTRY A,122(4),1011-1018.
MLA	Yang, Yunfan,et al."Theoretical Investigation of the Reaction Mechanism of Photodeamination Induced by Excited-State Intramolecular Proton Transfer of Cresol Derivatives".JOURNAL OF PHYSICAL CHEMISTRY A 122.4(2018):1011-1018.