51. Femtosecond studies of charge-transfer mediated proton transfer in 2-butylamino-6-methyl-4-nitropyridine N-oxide.
- Author
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Poór B, Michniewicz N, Kallay M, Buma WJ, Kubinyi M, Szemik-Hojniak A, Deperasiñska I, Puszko A, and Zhang H
- Subjects
- Computer Simulation, Molecular Conformation, Molecular Structure, Solvents chemistry, Time Factors, Protons, Pyridines chemistry, Quantum Theory
- Abstract
We have unraveled the effects of an amino substituent in the ortho position on the excited-state dynamics of 4-nitropyridine N-oxide by studying the picosecond fluorescence kinetics and femtosecond transient absorption of a newly synthesized compound, 2-butylamino-6-methyl-4-nitropyridine N-oxide, and by quantum chemical calculations. Similar to the parent compound, the S(1) state of the target molecule has significant charge-transfer character and shows a large (approximately 8000 cm(-1)) static Stokes shift in acetonitrile. Analysis of the experimental and the theoretical results leads, however, to a new scenario in which this intramolecular charge transfer triggers in polar, aprotic solvents an ultrafast (around 100 fs) intramolecular proton transfer between the amino and the N-O group. The electronically excited N-OH tautomer is subsequently subject to solvent relaxation and decays with a lifetime of approximately 150 ps to the ground state.
- Published
- 2006
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