Femtosecond dynamics of intramolecular photoinduced proton transfer in <Emphasis Type="Italic">N</Emphasis>-substituted 2-(2-aminophenyl)-4H-3,1-benzoxazin-4-ones |
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Authors: | M N Khimich F E Gostev I V Shelaev O M Sarkisov E A Birgen B M Bolotin B M Uzhinov |
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Institution: | 1.Moscow State University,Moscow,Russia;2.Semenov Institute of Chemical Physics,Russian Academy of Sciences,Moscow,Russia;3.Research Institute for Reagents and Ultra-High-Purity Chemicals,Moscow,Russia |
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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. |
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