Premium
TD‐DFT study on the sensing mechanism of a fluorescent chemosensor for fluoride: Excited‐state proton transfer
Author(s) -
Li GuangYue,
Zhao GuangJiu,
Liu YuHui,
Han KeLi,
He GuoZhong
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21466
Subject(s) - chemistry , fluorescence , intramolecular force , photochemistry , density functional theory , excited state , intermolecular force , imidazole , proton , acceptor , fluoride , hydrogen bond , singlet state , ground state , molecule , computational chemistry , inorganic chemistry , stereochemistry , atomic physics , organic chemistry , physics , quantum mechanics , condensed matter physics
An excited‐state proton transfer (ESPT) process, induced by both intermolecular and intramolecular hydrogen‐bonding interactions, is proposed to account for the fluorescence sensing mechanism of a fluoride chemosensor, phenyl‐1 H ‐anthra(1,2‐ d )imidazole‐6,11‐dione. The time‐dependent density functional theory (TD‐DFT) method has been applied to investigate the different electronic states. The present theoretical study of this chemosensor, as well as its anion and fluoride complex, has been conducted with a view to monitoring its structural and photophysical properties. The proton of the chemosensor can shift to fluoride in the ground state but transfers from the proton donor (NH group) to a proton acceptor (neighboring carbonyl group) in the first singlet excited state. This may explain the observed red shifts in the fluorescence spectra in the relevant fluorescent sensing mechanism. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010