TD-DFT study on the cyanide-chemosensing mechanism of 8-formyl-7-hydroxycoumarin
Proton transfer (PT) and excited-state PT process are proposed to account for the fluorescent sensing mechanism of a cyanide chemosensor, 8-formyl-7-hydroxycoumarin. The time-dependent density functional theory method has been applied to investigate the ground and the first singlet excited electroni...
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Published in | Journal of computational chemistry Vol. 32; no. 4; pp. 668 - 674 |
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Main Authors | , , , |
Format | Journal Article |
Language | English |
Published |
Hoboken
Wiley Subscription Services, Inc., A Wiley Company
01.03.2011
Wiley Subscription Services, Inc |
Subjects | |
Online Access | Get full text |
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Summary: | Proton transfer (PT) and excited-state PT process are proposed to account for the fluorescent sensing mechanism of a cyanide chemosensor, 8-formyl-7-hydroxycoumarin. The time-dependent density functional theory method has been applied to investigate the ground and the first singlet excited electronic states of this chemosensor as well as its nucleophilic addition product with cyanide, with a view to monitoring their geometries and spectrophotometrical properties. The present theoretical study indicates that phenol proton of the chemosensor transfers to the formyl group along the intramolecular hydrogen bond in the first singlet excited state. Correspondingly, the nucleophilic addition product undergoes a PT process in the ground state, and shows a similar structure in the first singlet excited state. This could explain the observed strong fluorescence upon the addition of the cyanide anion in the relevant fluorescent sensing mechanism. |
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Bibliography: | http://dx.doi.org/10.1002/jcc.21651 istex:707610EFB08BB9C8C85FE0DB60C1013A737E8603 NKBRSF - No. 2007CB815202 NSFC - No. 20833008 ArticleID:JCC21651 ark:/67375/WNG-S2RRX9B6-K ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0192-8651 1096-987X |
DOI: | 10.1002/jcc.21651 |