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.
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 S0 and S1 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.
authors.affiliation: Department of Theoretical Chemistry, Chemical Center, Lund University, P.O. Box 124, S-221 00 Lund, Sweden.
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Gaenko
authors.forename: Ajitha
authors.initials: A
authors.lastname: Devarajan
authors.forename: Rostislav E
authors.initials: RE
authors.lastname: Trifonov
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: Ostrovskii
mesh_terms: D005453:Fluorescence; D006863:Hydrogen-Ion Concentration; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010069:Oxadiazoles / Q000737:chemistry*; D013050:Spectrometry, Fluorescence
chemical_list: D010069:Oxadiazoles