Identifying the Role of Intramolecular Charge Transfer and Excited-State Proton Transfer in Fluorescence Mechanism for an Azido-Based Chemosensor

doi:10.1021/acs.jpcc.8b06185

	Identifying the Role of Intramolecular Charge Transfer and Excited-State Proton Transfer in Fluorescence Mechanism for an Azido-Based Chemosensor
	Li, Yang 1,2; Zhao, Ningjiu 1; Jia, Yan 1; Li, Peng 1
刊名	JOURNAL OF PHYSICAL CHEMISTRY C
	2018-11-22
卷号	122 期号:46 页码:26576-26583
ISSN号	1932-7447
DOI	10.1021/acs.jpcc.8b06185
通讯作者	Zhao, Ningjiu(zhaonj@dicp.ac.cn) ; Li, Peng(pengl@dicp.ac.cn)
英文摘要	In the present work, the fluorescence enhancement mechanism of H2S chemosensor 2-(2-azidophenyl)-1-(p-tolyl)-1H-phenanthro[9,10-d]imidazole (P-N3) has been investigated in detail by the density functional theory (DFT) and time-dependent DFT (TDDFT) methods. The excitation/emission energies which were calculated using the TDDFT method can simulate the experimental spectra well. The potential energy barrier of ca. 10 kcal/mol for the forward excited-state intramolecular proton transfer (ESIPT) and that of <2 kcal/mol for the reversed ESIPT of the product of the chemosensor sensing H2S (P-NH2) have been estimated, respectively. It shows that the reversed ESIPT can occur more easily than the forward one, and the proton-transferred tautomer (P-NH2-PT) is supposed to be not the dominant emission species in this system. In addition, by analyzing the electronic and geometrical structures, the large Stokes-shift observed in the experiment is regarded to be derived from a significant geometry rearrangement upon photoexcitation. Furthermore, when comparing P-NH2 with P-N3, it is found that in the first singlet excited state the twisting is not energetically favorable for P-NH2, whereas P-N3 can easily twist in which the intersystem crossing can occur, that is responsible for the weak fluorescence of P-N3. The results shed light on the photophysics of azido-based chemosensors and help to inspire the design for novel chemosensors.
资助项目	National Natural Science Foundation of China[21703244] ; National Natural Science Foundation of China[21673237] ; National Natural Science Foundation of China[21533010] ; DICP Outstanding Postdoctoral Foundation[2016YB09] ; China Postdoctoral Science Foundation[2017M611276]
WOS关键词	HYDROGEN-SULFIDE ; TD-DFT ; SENSING MECHANISM ; ESIPT ; PROBE ; H2S ; CHROMOPHORES ; ACTIVATION ; CONTINUUM ; MEDIATOR
WOS研究方向	Chemistry ; Science & Technology - Other Topics ; Materials Science
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000451495600032
资助机构	National Natural Science Foundation of China ; National Natural Science Foundation of China ; DICP Outstanding Postdoctoral Foundation ; DICP Outstanding Postdoctoral Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; DICP Outstanding Postdoctoral Foundation ; DICP Outstanding Postdoctoral Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; DICP Outstanding Postdoctoral Foundation ; DICP Outstanding Postdoctoral Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; DICP Outstanding Postdoctoral Foundation ; DICP Outstanding Postdoctoral Foundation ; China Postdoctoral Science Foundation ; China Postdoctoral Science Foundation
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/166602]
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	Zhao, Ningjiu; Li, Peng
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Li, Yang,Zhao, Ningjiu,Jia, Yan,et al. Identifying the Role of Intramolecular Charge Transfer and Excited-State Proton Transfer in Fluorescence Mechanism for an Azido-Based Chemosensor[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2018,122(46):26576-26583.
APA	Li, Yang,Zhao, Ningjiu,Jia, Yan,&Li, Peng.(2018).Identifying the Role of Intramolecular Charge Transfer and Excited-State Proton Transfer in Fluorescence Mechanism for an Azido-Based Chemosensor.JOURNAL OF PHYSICAL CHEMISTRY C,122(46),26576-26583.
MLA	Li, Yang,et al."Identifying the Role of Intramolecular Charge Transfer and Excited-State Proton Transfer in Fluorescence Mechanism for an Azido-Based Chemosensor".JOURNAL OF PHYSICAL CHEMISTRY C 122.46(2018):26576-26583.