Electronic and steric substituent effects on the fluorescence emission of 2-pyrazoline derivatives

A series of substituted 2-pyrazolines were synthesized, and the steric and electronic effects of substituents on the C₃ - and C₅ -positions of the heterocyclic ring on their fluorescent ability were investigated. Two different conjugative intramolecular charge transfer (ICT) and intramolecular charge transfer through space (spiro-conjugation) affect the fluorescence intensity of these compounds. The extent of the ICT process and spiro-conjugation depends on the electronic nature of the additional substitution and its position on the attached aryl rings. In addition, the effects of the concentration and the solvent polarity on the fluorescence emission were studied. Density functional theory (DFT) calculations were carried out to gain insight into the geometric, electronic, and spectroscopic properties of the pyrazoline derivatives. The results of both experimental and computational studies explain the effects of the geometrical orientation of the C₃ - and C₅ -aryl rings toward the heterocyclic ring and also the electronic nature of their additional substitutions on the fluorescence intensity.