Der Substituenteneinfluß auf die Fluoreszenz des 1.3-Diphenyl-2-pyrazolins / Substituent Effects on the Fluorescence of 1,3-Diphenyl-2-pyrazoline

Abstract

The electronic absorption spectra, absolute fluorescence spectra and fluorescence quantum yields as well as the fluorescence decay times of nine 1,3-diphenyl-2-pyrazolines substituted in the para-position of the 1-phenyl ring and of 19 substituted in the paraposition of the 3-phenyl ring were measured in degassed benzene at room temperature. The fluorescence quantum yields are about 0.90 with the exception of the NO2- and J-substituted 1,3-diphenyl-2-pyrazolines. The fluorescence decay time ranges from 2 to 4 nsec. The natural fluorescence lifetimes determined experimentally agree well with those calculated from the absorption spectra according to STRICKLER and BERG. A plot of the Hammett σp-values versus the energies of the absolute fluorescence maxima of the psubstituted 1- and 3-phenyl ring of the 2-pyrazoline system shows a statistically significant linear correlation with moderate precision. The linearity between ground state substituent constants and fluorescence energies reveals that the relative importance of the inductive and the resonance effects of the substituents remains constant during the transition from the ground state to the relaxed excited singlet state. In the excited singlet state of 1,3-diphenyl-2-pyrazoline the p-substituents provide more room for a larger charge displacement in the intramolecular charge-transfer. The structural bands in the fluorescence spectra resulting from strong electron accepting substituents in the para-position of the 1-phenyl ring are considered as the result of the ring breathing vibration due to a local excitation of the 1-phenyl ring.