Experimental and theoretical spectroscopic studies of ortho derivatives of methyl p-dimethylaminobenzoate

Steady-state spectroscopic studies of two ortho (–OCH3 and –OH) derivatives of methyl p-dimethylaminobenzoate have been performed. The absorption spectra of molecules under study are analyzed taking into consideration results of quantum chemical semiempirical calculations. The fluorescence spectra of these molecules possess in polar solvents two bands, i.e., the locally excited and intramolecular charge transfer (ICT) fluorescence band. Their intensity ratio as well as the fluorescence/phosphorescence intensity ratio determined at 77 K depends on the solvent polarity. Theoretical studies of the TICT phenomenon have been made in order to explain the dual emission of molecules under study. Calculated electric dipole moments of these molecules in the ground, S0, and excited, S1(LE) and S1(ICT) states, have been compared with experimentally determined data. Theoretically determined transition energies, ΔEi, oscillator strengths, fi, and electric dipole moments image, image and image of the planar donor–acceptor (D/A) conformer agree with experimental data. According to Marcus theory inner- and outer-solvatation sphere reorganization energies (λout, λin) are calculated using the determined spectroscopic properties of molecules under study.