Femtosecond dynamics of intramolecular photoinduced proton transfer in N-substituted 2-(2-aminophenyl)-4H-3,1-benzoxazin-4-ones

Abstract

Femtosecond dynamics of processes in the excited state of 2-(2-aminophenyl)-4H-3,1-benzoxazin-4-ones has been studied by femtosecond absorption spectroscopy. The rate constants of intramolecular photoinduced proton transfer (IPPT) have been determined for the N-substituted derivatives (0.7–11 ps−1). The IPPT rate constant depends on the inductive constant of the substituent and the potential barrier height, which was calculated by a quantum-chemical method (TDDFT). The multiexponential character of the kinetics of photoinduced absorption by the compounds with a low inductive constant of the N-substituent in the spectral region of the S1 → SN absorption and the stimulated emission of the IPPT product is explained by the rapid (∼10 ps−1) relaxation process preceding the IPPT.