A theoretical study of the ESIPT mechanism of 3-hydroxyflavone derivatives: solvation effect and the importance of TICT for its dual fluorescence properties

doi:10.1039/c9qo00634f

	A theoretical study of the ESIPT mechanism of 3-hydroxyflavone derivatives: solvation effect and the importance of TICT for its dual fluorescence properties
	Qi, Yutai 2; Lu, Meiheng 3,4; Wang, Yi 2; Tang, Zhe 5; Gao, Ziqing 2; Tian, Jing 2; Fei, Xu 1; Li, Yao 6; Liu, Jianyong 3
刊名	ORGANIC CHEMISTRY FRONTIERS
	2019-09-07
卷号	6 期号:17 页码:3136-3143
ISSN号	2052-4129
DOI	10.1039/c9qo00634f
通讯作者	Wang, Yi(wangyi@dlpu.edu.cn) ; Liu, Jianyong(beam@dicp.ac.cn)
英文摘要	In this paper, the excited-state intramolecular proton transfer (ESIPT) process and the solvatochromic effect of 2-(4-(diethylamino)phenyl)-3-hydroxy-4H-chromen-4-one (DHC) molecules were reported by the density functional theory and time-dependent density functional theory method. We optimized the structures in four kinds of solvents, and the recorded absorption and fluorescence spectra were in agreement with the experiments. By establishing the potential energy curve, we proved that this fluorescent probe was designed based on the ESIPT process of the parent molecule DHC. A deeper study of the ESIPT process revealed that the energy consumed by the molecules along the C5-C18 bond twist was an important part of the dual fluorescence characteristics of the DHC, and the geometric structure tended to be planar with the decrease of the dielectric constant of the solvent. The effect of solvent media on electronic transition energies and absorption as well as florescence spectra were presented. As we know, a driving force of the proton transfer reaction was provided by hydrogen bonding. By comparing the infrared vibration spectrum, bond length and bond angle, we found that the hydrogen bond was enhanced after photoexcitation and was gradually increased as the solvent dielectric constant decreased (dimethylsulfoxide (DMSO) < acetonitrile (ACN) < dichloromethane (DCM) < 1,4-dioxane (DIO)), which was also evidenced by the reduced density gradient function (RDG) isosurface and scatter plots. Therefore, the process of ESIPT reaction was controlled by the solvent. Furthermore, the effect of the solvent on ESIPT was explained by comparing the reaction energy barrier in four kinds of solvents. The results showed that ESIPT was more likely to occur as the solvent dielectric constant decreased.
资助项目	Liaoning Province Natural Science Foundation[20180550765] ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; National Natural Science Foundation of China[31771914]
WOS关键词	INTRAMOLECULAR PROTON-TRANSFER ; GAUSSIAN-BASIS SETS ; EXCITED-STATE ; CHARGE-TRANSFER ; TRANSITION-STATES ; ELECTRON-TRANSFER ; ATOMS LI ; SOLVENTS ; FLUORIDE ; PROBES
WOS研究方向	Chemistry
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000483840200011
资助机构	Liaoning Province Natural Science Foundation ; Liaoning Province Natural Science Foundation ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Liaoning Province Natural Science Foundation ; Liaoning Province Natural Science Foundation ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Liaoning Province Natural Science Foundation ; Liaoning Province Natural Science Foundation ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; Liaoning Province Natural Science Foundation ; Liaoning Province Natural Science Foundation ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; Open Project of SKLMRD-K2019 (Open Project of the State Key Laboratory of Molecular Reaction Dynamics) ; National Natural Science Foundation of China ; National Natural Science Foundation of China
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/172963]
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	Wang, Yi; Liu, Jianyong
作者单位	1.Dalian Polytech Univ, Network Informat Ctr, Dalian, Peoples R China 2.Dalian Polytech Univ, Sch Biol Engn, Dalian 116034, Peoples R China 3.Chinese Acad Sci, State Key Lab Mol React Dynam, Dalian Inst Chem Phys, Dalian 116023, Peoples R China 4.Shenyang Univ Chem Technol, Coll Appl Chem, Shenyang 110142, Liaoning, Peoples R China 5.Shandong Univ, Inst Mol Sci & Engn, Qingdao 266237, Shandong, Peoples R China 6.Dalian Polytech Univ, Sch Light Ind & Chem Engn, Dalian, Peoples R China
推荐引用方式 GB/T 7714	Qi, Yutai,Lu, Meiheng,Wang, Yi,et al. A theoretical study of the ESIPT mechanism of 3-hydroxyflavone derivatives: solvation effect and the importance of TICT for its dual fluorescence properties[J]. ORGANIC CHEMISTRY FRONTIERS,2019,6(17):3136-3143.
APA	Qi, Yutai.,Lu, Meiheng.,Wang, Yi.,Tang, Zhe.,Gao, Ziqing.,...&Liu, Jianyong.(2019).A theoretical study of the ESIPT mechanism of 3-hydroxyflavone derivatives: solvation effect and the importance of TICT for its dual fluorescence properties.ORGANIC CHEMISTRY FRONTIERS,6(17),3136-3143.
MLA	Qi, Yutai,et al."A theoretical study of the ESIPT mechanism of 3-hydroxyflavone derivatives: solvation effect and the importance of TICT for its dual fluorescence properties".ORGANIC CHEMISTRY FRONTIERS 6.17(2019):3136-3143.