Optical absorption of 1-phenyl-3-methyl-1H-pyrazolo[3,4-b]quinoline derivatives: Molecular dynamics modeling

Paper deals with quantum chemical modeling of the optical absorption spectra of 6-fluoro, 7-trifluoromethyl, 6-cyano, 6-carboethoxy and 6-tert-butyl derivatives of 1-phenyl-3-methyl-1H-pyrazolo3,4-b]quinoline. The calculations are performed by means of the semiempirical quantum chemical methods (AM1 or PM3) applied to the equilibrium molecular conformation in vacuo (T = 0 K) or molecular dynamic (MD) trajectories as obtained within fragmental or total MD simulations at T = 300 K. The results of these calculations are compared with the measured spectra of optical absorption. The quantum chemical analysis show that the dynamics of the methyl, trifluoromethyl, carboethoxy and tert-butyl groups practically does not influence the absorption spectra whereas the strongest their modifications are found to be related with dynamics of the aromatic group. The semiempirical method AM1 in combination with MD simulations gives for all dyes the best agreement between the calculated and measured spectral positions of absorption bands. In most cases the quantum chemical calculations describe properly the trends of their changes depending on the lateral substituent.