Sensing mechanism for a fluorescent off-on chemosensor for cyanide anion

doi:10.1016/j.jlumin.2016.07.024

	Sensing mechanism for a fluorescent off-on chemosensor for cyanide anion
	Chen, Junsheng 1; Li, Yang 1,3; Chu, Tian-Shu 1,2
刊名	JOURNAL OF LUMINESCENCE
	2016-11-01
卷号	179 页码:203-210
关键词	Sensing Mechanism Density Functional Calculations Intramolecular Charge Transfer
ISSN号	0022-2313
DOI	10.1016/j.jlumin.2016.07.024
文献子类	Article
英文摘要	In this article, the sensing mechanism of cyanide anion chemosensor 2((2-phenyl-2H-1,2,3-triazol-4-yl) methylene)malononitrile (M1) has been investigated through the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The theoretical results demonstrate that the reaction barrier of 13.02 kcal/mol means a favorable response speed of the chemosensor M1 for cyanide anion. Cyanide anion attacks C=C double bond and hinders the ICT process from the malononitrile moiety to the fluorophore phenyl ring. The high viscosity of DMSO restrains the twisting of the group, inhibits the formation of the ICT state in the first excited state. Due to weak ICT character, the nucleophilic addition product shows the dramatic "off-on" fluorescence enhancement. Meanwhile, intramolecular charge transfer (ICT) mechanism accounts for how different solvents influence the fluorescence spectra. That is, more obvious ICT character of product in EtOH causes fluorescence quenching. The "reaction-based" recognition mode and large bond energy between M1 and cyanide anion minimize the interference by other anions, such as F-, AcO-. Thus, the chemosensor M1 has a high selectivity for cyanide. (C) 2016 Elsevier B.V. All rights reserved.
WOS关键词	INTRAMOLECULAR CHARGE-TRANSFER ; PHOTOINDUCED ELECTRON-TRANSFER ; ULTRAFAST TWISTING DYNAMICS ; DENSITY-FUNCTIONAL THEORY ; STATE PROTON-TRANSFER ; SET MODEL CHEMISTRY ; GAUSSIAN-BASIS SETS ; EXCITED-STATE ; LIVING CELLS ; TOTAL ENERGIES
WOS研究方向	Optics
语种	英语
出版者	ELSEVIER SCIENCE BV
WOS记录号	WOS:000384384800029
内容类型	期刊论文
源URL	[http://cas-ir.dicp.ac.cn/handle/321008/170158]
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	Chu, Tian-Shu
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, 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.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Chen, Junsheng,Li, Yang,Chu, Tian-Shu. Sensing mechanism for a fluorescent off-on chemosensor for cyanide anion[J]. JOURNAL OF LUMINESCENCE,2016,179:203-210.
APA	Chen, Junsheng,Li, Yang,&Chu, Tian-Shu.(2016).Sensing mechanism for a fluorescent off-on chemosensor for cyanide anion.JOURNAL OF LUMINESCENCE,179,203-210.
MLA	Chen, Junsheng,et al."Sensing mechanism for a fluorescent off-on chemosensor for cyanide anion".JOURNAL OF LUMINESCENCE 179(2016):203-210.