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ID 32964
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Author
Xie, Guobin
Yamamoto, Shunzo
Abstract

The emission spectra of toluene (T)–triethylamine (TEA) systems were measured under conditions of steady-state illumination in some protic and aprotic solvent–THF mixtures. The fluorescence spectrum of the T–TEA system in THF could be separated into three component bands (band A at 279 nm (fluorescence of T), band B at 336 nm (fluorescence of TEA) and band C at 373 nm (emission from an intermolecular exciplex)). The intensities of bands B and C decreased with increasing solvent polarity. The decrease in the intensities of bands B and C is considered to be caused by the enhanced conversion of the exciplex to an ion-pair with increase in solvent polarity. The intensities of bands B and C also decreased owing to the hydrogen-bonding interaction between TEA and protic solvents, but in this case the intensity of band A increased. Acetonitrile only has a polar effect and trichloroacetic acid only has a hydrogen-bonding (or protonation) effect, while alcohols have both effects. The equilibrium constants for the formation of intermolecular hydrogen-bonded complexes of TEA with alcohols were estimated from the changes in the intensity of band A. The hydrogen-bonding and polar effects of alcohols on the intensities of bands B and C could be evaluated separately. The ratio of the hydrogen-bonding effect to the polar effect of alcohols was observed to increase with increasing vol.% of alcohol.

Keywords
solvent effect
polar effect
hydrogen-bonding
fluorescence
exciplex
Note
Digital Object Identifer:10.1016/S1010-6030(03)00413-1
Published with permission from the copyright holder. This is the institute's copy, as published in the Journal of Photochemistry and Photobiology a-Chemistry, March 2004, Volume 162, Issue 2-3, Pages 449-456.
Publisher URL:http://dx.doi.org/10.1016/S1010-6030(03)00413-1
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Copyright © 2004 Elsevier B.V. All rights reserved.
Published Date
2004-3
Publication Title
Journal of Photochemistry and Photobiology A: Chemistry
Volume
volume162
Issue
issue2-3
Start Page
449
End Page
456
Content Type
Journal Article
language
英語
Refereed
True
DOI
Web of Science KeyUT
Submission Path
chemistry_general/3