Photoluminescence of 1,3-dimethyl pyrazoloquinoline derivatives

This paper presents absorption and photoluminescence of 6-F, 6-Br, 6-Cl, 7-TFM and 6-COOEt derivatives of 1,3-dimethyl-1H-Pyrazolo[3,4-b]quinoline (DMPQ). The measured absorption and emission spectra are compared with the quantum chemical calculations performed by means of the semi-empirical methods (AM1 or PM3) that are applied either to the equilibrium conformations in vacuo (T = 0 K) or combined with the molecular dynamics simulations (T = 300 K). The spectra calculated by the AM1 method appear to be for all dyes in practically excellent agreement with the measured ones. In particular, the position of the first absorption band is obtained with the accuracy up to a few nanometers, whereas the calculated photoluminescence spectra predict the positions of the emission maxima for a gas phase with the accuracy up to 10–18 nm. The photoemission spectra of DMPQ dyes are considerably less solvatochromic comparing to phenyl-containing pyrazoloquinoline derivatives. According to the quantum chemical analysis the reason for such behaviour lies in a local character of the electronic transitions of DMPQ dyes which are characterized by a relatively small difference between the excited state and ground state dipole moments. Importantly that the rotational dynamics of both methyl subunits does not change this situation.