Sensing mechanism for a fluoride chemosensor: invalidity of excited-state proton transfer mechanism

被引：90

作者：

Chen, Jun-Sheng ^{[1
,2
]}

Zhou, Pan-Wang ^{[1
]}

Yang, Song-Qiu ^{[1
]}

Fu, Ai-Ping ^{[3
]}

Chu, Tian-Shu ^{[1
,3
]}

机构：

[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

[3] Qingdao Univ, Growing Base State Key Lab, Lab New Fiber Mat & Modern Text, Inst Computat Sci & Engn, Qingdao 266071, Peoples R China

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2013年 / 15卷 / 38期

基金：

中国国家自然科学基金;

关键词：

PHOTOINDUCED ELECTRON-TRANSFER; DENSITY-FUNCTIONAL THEORY; DUAL OUTPUT MODES; AQUEOUS-MEDIA; TD-DFT; FLUORESCENT CHEMOSENSOR; IDENTITY APPROXIMATION; RELAY RECOGNITION; DERIVATIVES; SENSOR;

D O I：

10.1039/c3cp51482j

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Our density functional theory (DFT)/time-dependent DFT calculations for the fluoride anion sensor, 5,7-dibromo-8-tert-butyldimethylsilyloxy-2-methylquinoline (DBM), suggested a different sensing mechanism from the experimentally proposed one (Chem. Commun., 2011, 47, 7098). Instead of the formation of fluoride-hydrogen-bond complex (DBMOHF) and excited-state proton transfer mechanism, the theoretical results predicted a sensing mechanism based on desilylation reaction and intramolecular charge transfer (ICT). The fluoride anion reacted with DBM and formed an anion (DBMO), with the ICT causing a red shift in the absorbance and emission spectra of the latter. The calculated vertical excitation energies in the ground and first excited states of both DBM and DBMO, as well as the calculated H-1 NMR spectra, significantly reproduced the experimental measurements, providing additional proofs for our proposed sensing mechanism for DBM.

引用

页码：16183 / 16189

页数：7

共 51 条

[1] ELECTRONIC-STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS - THE PROGRAM SYSTEM TURBOMOLE [J].