Mechanism of Excited-State Intramolecular Proton Transfer for 1,2-Dihydroxyanthraquinone: Effect of Water on the ESIPT

	Mechanism of Excited-State Intramolecular Proton Transfer for 1,2-Dihydroxyanthraquinone: Effect of Water on the ESIPT
	Sunt, Shuang 1; Peng, Yajing 1,2; Xiu, Xianming 1; Ye, Yuqing 1
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2017-08-03
卷号	121 期号:30 页码:5625-5634
英文摘要	Mechanisms of excited-state intramolecular proton transfer (ESIPT) of 1,2-dihydroxyanthraquinone (ALR) in ethanol solvent and binary solvent of water and ethanol are investigated using the density functional theory and time-dependent density functional theory. The intramolecular hydrogen bond is found to be reinforced in the excited state based on the bond lengths, bond angles, and infrared vibrational spectra of relevant group. The reinforcement of intramolecular hydrogen bond is attributed to the charge transfer in the excited state, which leads the ESIPT to form a keto isomer. The absorption and fluorescence spectra of ALR in binary solvent with different water percentage are obtained and demonstrate the inhibition effect of water on the ESIPT process, which are consistent with the experimentally observation. Furthermore, more water molecules are considered near the carbonyl group and hydroxyl group related to the intramolecular proton transfer to form intermolecular hydrated hydrogen bond with ALR for clarifying the block mechanism of water on ESIPT. The potential energy curves, frontier molecular orbitals, and NBO analysis are calculated-for the several complexes in the ground and excited states. The results show that the interrupt role of water on the ESIPT originated from the forming of hydrated hydrogen bond between the carbonyl oxygen atom and the water molecule, which weakens the intramolecular hydrogen bond associated with proton transfer, increases the energy barrier of ESIPT, and thus precludes the transition of ALR-E to ALR-K in the excited state. In addition, the weakening of intramolecular hydrogen bonds is increased as the water molecule number increases. So the inhibitory effect is enhanced by the water quantity, which reasonably explains the experimental attenuating of keto emission spectra as the water percentage in binary solvent increases.
WOS标题词	Science & Technology ; Physical Sciences
类目[WOS]	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
研究领域[WOS]	Chemistry ; Physics
关键词[WOS]	PHOTOINDUCED ELECTRON-TRANSFER ; DENSITY-FUNCTIONAL THEORY ; TD-DFT ; SENSING MECHANISM ; FLUORESCENCE ; METHANOL ; COMPLEX ; PHOTOCHEMISTRY ; APPROXIMATION ; PEROXYNITRITE
收录类别	SCI
语种	英语
WOS记录号	WOS:000407188800007
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/149817]
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
作者单位	1.Bohai Univ, Dept Phys, JinZhou 121013, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
推荐引用方式 GB/T 7714	Sunt, Shuang,Peng, Yajing,Xiu, Xianming,et al. Mechanism of Excited-State Intramolecular Proton Transfer for 1,2-Dihydroxyanthraquinone: Effect of Water on the ESIPT[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2017,121(30):5625-5634.
APA	Sunt, Shuang,Peng, Yajing,Xiu, Xianming,&Ye, Yuqing.(2017).Mechanism of Excited-State Intramolecular Proton Transfer for 1,2-Dihydroxyanthraquinone: Effect of Water on the ESIPT.JOURNAL OF PHYSICAL CHEMISTRY A,121(30),5625-5634.
MLA	Sunt, Shuang,et al."Mechanism of Excited-State Intramolecular Proton Transfer for 1,2-Dihydroxyanthraquinone: Effect of Water on the ESIPT".JOURNAL OF PHYSICAL CHEMISTRY A 121.30(2017):5625-5634.