Optical absorption of 1,3-diphenyl-1H-Pyrazolo[3,4-b]quinoline and its derivatives

Abstract

Paper deals with the experimental investigations and quantum chemical calculations of the absorption spectra of newly synthesized 1,3-diphenyl-1H-Pyrazolo[3,4-b]quinoline and its 6-Vinyl, 6-N,N-Diphenyl, 6-Methyl, 6-Fluoro, 6-Bromo, and 6-Chloro derivatives. The calculations are performed by means of the semiempirical quantum chemical methods AM1 or PM3 combined with: (a) equilibrium molecular conformation (EMC) in vacuo; (b) the molecular conformation model considering a dynamical rotation of phenyl rings only (T = 300 K); and (c) the most general model of the conformational molecular dynamics (MD) at T = 300 K. It is shown that the phenyl dynamics appears to be not important in the spectral position of absorption thresholds as well as in a broadening of most absorbtion bands. On the other hand, the MD simulations reproduce a broadening of the absorbtion spectra as well as the electron-vibronic coupling leading to a red-shift of absorption bands with increasing of temperature. The conformational MD model in combination with the quantum chemical AM1 method gives in most cases the best agreement with the experimental data, namely in the sense of spectral positions and width of the absorption bands including first oscillators (absorption thresholds). © 2006 Elsevier B.V. All rights reserved.