DFT/TDDFT Study on the Sensing Mechanism of a Fluorescent Probe for Hydrogen Sulfide: Excited State Intramolecular Proton Transfer Coupled Twisted Intramolecular Charge Transfer

	DFT/TDDFT Study on the Sensing Mechanism of a Fluorescent Probe for Hydrogen Sulfide: Excited State Intramolecular Proton Transfer Coupled Twisted Intramolecular Charge Transfer
	Li, Yang 1,3; Chu, Tian-Shu 2,3
刊名	JOURNAL OF PHYSICAL CHEMISTRY A
	2017-07-20
卷号	121 期号:28 页码:5245-5256
英文摘要	By using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, the sensing mechanism of a fluorescent probe 2-(2-hydroxyphenyl) benzothiazole (HBT) derivative HBTPP-S for hydrogen sulfide has been thoroughly studied. The thiolysis reaction has a moderate reaction barrier of 18.40 kcal mol(-1), which indicates that the hydrogen sulfide sensing process has a favorable response speed. Because of the nonradiative donor-excited photoinduced electron transfer (d-PET, fluorophore as the electron donor) from the excited HBTPP group to the electron-withdrawing 2,4-dinitrophenyl group, as well as the inhibition of the proton transfer (PT) and the excited state intramolecular proton transfer (ESIPT) process by 2,4-dinitrophenyl group, the probe HBTPP-S is essentially nonfluorescent. On the other hand, the added hydrogen sulfide induces the thiolysis of the 2,4-dinitrophenyl ether bond, and then the thiolysis product HBTPP comes into existence. The theoretically simulated potential energy surface demonstrates that without the electron-withdrawing 2,4-dinitrophenyl group, the thiolysis product HBTPP undergoes the excited state intramolecular proton transfer (ESIPT) coupled twisted intramolecular charge transfer (TICT) processes in the first excited state. The absence of the d-PET and the process mentioned above may explain the significant fluorescent turn-on response and large Stokes shift of the thiolysis product HBTPP.
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 ; GAUSSIAN-BASIS SETS ; LIVING CELLS ; TD-DFT ; ANISOTROPIC DIELECTRICS ; FEMTOSECOND DYNAMICS ; SELECTIVE DETECTION ; OPTICAL-PROPERTIES ; TRANSFER ESIPT ; REDOX CYCLE
收录类别	SCI
语种	英语
WOS记录号	WOS:000406357000002
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/149936]
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.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 2.Qingdao Univ, Inst Computat Sci & Engn, Lab New Fiber Mat & Modern Text, Growing Base State Key Lab, Qingdao 266071, Peoples R China 3.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	Li, Yang,Chu, Tian-Shu. DFT/TDDFT Study on the Sensing Mechanism of a Fluorescent Probe for Hydrogen Sulfide: Excited State Intramolecular Proton Transfer Coupled Twisted Intramolecular Charge Transfer[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2017,121(28):5245-5256.
APA	Li, Yang,&Chu, Tian-Shu.(2017).DFT/TDDFT Study on the Sensing Mechanism of a Fluorescent Probe for Hydrogen Sulfide: Excited State Intramolecular Proton Transfer Coupled Twisted Intramolecular Charge Transfer.JOURNAL OF PHYSICAL CHEMISTRY A,121(28),5245-5256.
MLA	Li, Yang,et al."DFT/TDDFT Study on the Sensing Mechanism of a Fluorescent Probe for Hydrogen Sulfide: Excited State Intramolecular Proton Transfer Coupled Twisted Intramolecular Charge Transfer".JOURNAL OF PHYSICAL CHEMISTRY A 121.28(2017):5245-5256.