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The fluorescence lifetimes of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) were determined in a large number of solvents and solvent mixtures, displaying variations from 825 ns in CD3CN to 13 ns in CHCl3. Large deuterium isotope effects (8-11) and significant activation energies (generally 2-15 kJ mol-1) for fluorescence quenching of DBO are observed, which support a novel solvent-induced quenching mechanism via an aborted hydrogen atom transfer. In CCl4 a photoinduced electron-transfer quenching mechanism may compete. The fluorescence quenching by solvent mixtures is not proportional to the mole fraction of the two components, indicating a preferential solvation of the excited state.

Nau, W.M., Gerhard, G., Hermann, R., Julia, W., Olivucci, M., Scaiano, J.C. (1999). Fluorescence of 2,3-Diazabicyclo[2.2.2]oct-2-ene Revisited:  Solvent-Induced Quenching of the n,π*-Excited State by an Aborted Hydrogen Atom Transfer. JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY, 103(11), 1579-1584 [10.1021/jp984303f].

Fluorescence of 2,3-Diazabicyclo[2.2.2]oct-2-ene Revisited:  Solvent-Induced Quenching of the n,π*-Excited State by an Aborted Hydrogen Atom Transfer

Olivucci, Massimo;
1999-01-01

Abstract

The fluorescence lifetimes of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) were determined in a large number of solvents and solvent mixtures, displaying variations from 825 ns in CD3CN to 13 ns in CHCl3. Large deuterium isotope effects (8-11) and significant activation energies (generally 2-15 kJ mol-1) for fluorescence quenching of DBO are observed, which support a novel solvent-induced quenching mechanism via an aborted hydrogen atom transfer. In CCl4 a photoinduced electron-transfer quenching mechanism may compete. The fluorescence quenching by solvent mixtures is not proportional to the mole fraction of the two components, indicating a preferential solvation of the excited state.
1999
Nau, W.M., Gerhard, G., Hermann, R., Julia, W., Olivucci, M., Scaiano, J.C. (1999). Fluorescence of 2,3-Diazabicyclo[2.2.2]oct-2-ene Revisited:  Solvent-Induced Quenching of the n,π*-Excited State by an Aborted Hydrogen Atom Transfer. JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY, 103(11), 1579-1584 [10.1021/jp984303f].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11365/32715
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