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Spectral and density functional studies on the absorbance and fluorescence spectra of 2-R-5-phenyl-1,3,4-oxadiazoles and their conjugate acids

Gaenko, Alexander LU ; Devarajan, Ajitha LU ; Trifonov, Rostislav E and Ostrovskii, Vladimir A (2006) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 110(28). p.8750-8757
Abstract
Absorption and fluorescence spectra of 2-R-5-phenyl-1,3,4-oxadiazoles (R = H, methyl, tert-butyl, trifluoromethyl, amino, phenyl, benzyl) were studied experimentally and by time dependent density functional theory (TDDFT) methods. In acidic media a substantial red shift is observed due to the presence of conjugate acid forms. Two conjugate acid forms (3H and 4H) are possible for unsymmetrically substituted oxadiazoles. Relative basicities of the two basic centers of oxadiazole ring at the S-0 and S-1 geometries were calculated using the local density descriptors approach. Substituent effects were studied by analyzing the electron density distribution in the ground and excited states. Analyzing the absorption spectra and local descriptors... (More)
Absorption and fluorescence spectra of 2-R-5-phenyl-1,3,4-oxadiazoles (R = H, methyl, tert-butyl, trifluoromethyl, amino, phenyl, benzyl) were studied experimentally and by time dependent density functional theory (TDDFT) methods. In acidic media a substantial red shift is observed due to the presence of conjugate acid forms. Two conjugate acid forms (3H and 4H) are possible for unsymmetrically substituted oxadiazoles. Relative basicities of the two basic centers of oxadiazole ring at the S-0 and S-1 geometries were calculated using the local density descriptors approach. Substituent effects were studied by analyzing the electron density distribution in the ground and excited states. Analyzing the absorption spectra and local descriptors results, we predict 4H forms to be the dominant acid forms. Calculated emission peaks of 4H forms agree well with experimental observations. An abnormal red shift in the case of the 3H forms is attributed to the increased stabilization of the N-H bond in the 3H forms compared to the 4H forms. (Less)
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publication status
published
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in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
110
issue
28
pages
8750 - 8757
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000239001600019
  • scopus:33746892236
ISSN
1520-5215
DOI
10.1021/jp061174r
language
English
LU publication?
yes
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The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
2d7b23a0-5952-42b6-b3c3-a2451b4f4a97 (old id 402130)
date added to LUP
2016-04-01 16:50:59
date last changed
2021-02-17 05:58:54
@article{2d7b23a0-5952-42b6-b3c3-a2451b4f4a97,
  abstract     = {Absorption and fluorescence spectra of 2-R-5-phenyl-1,3,4-oxadiazoles (R = H, methyl, tert-butyl, trifluoromethyl, amino, phenyl, benzyl) were studied experimentally and by time dependent density functional theory (TDDFT) methods. In acidic media a substantial red shift is observed due to the presence of conjugate acid forms. Two conjugate acid forms (3H and 4H) are possible for unsymmetrically substituted oxadiazoles. Relative basicities of the two basic centers of oxadiazole ring at the S-0 and S-1 geometries were calculated using the local density descriptors approach. Substituent effects were studied by analyzing the electron density distribution in the ground and excited states. Analyzing the absorption spectra and local descriptors results, we predict 4H forms to be the dominant acid forms. Calculated emission peaks of 4H forms agree well with experimental observations. An abnormal red shift in the case of the 3H forms is attributed to the increased stabilization of the N-H bond in the 3H forms compared to the 4H forms.},
  author       = {Gaenko, Alexander and Devarajan, Ajitha and Trifonov, Rostislav E and Ostrovskii, Vladimir A},
  issn         = {1520-5215},
  language     = {eng},
  number       = {28},
  pages        = {8750--8757},
  publisher    = {The American Chemical Society (ACS)},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Spectral and density functional studies on the absorbance and fluorescence spectra of 2-R-5-phenyl-1,3,4-oxadiazoles and their conjugate acids},
  url          = {http://dx.doi.org/10.1021/jp061174r},
  doi          = {10.1021/jp061174r},
  volume       = {110},
  year         = {2006},
}