Wm. Nau et al., Fluorescence of 2,3-diazabicyclo[2.2.2]oct-2-ene revisited: Solvent-induced quenching of the n,pi*-excited state by an aborted hydrogen atom transfer, J PHYS CH A, 103(11), 1999, pp. 1579-1584
The fluorescence lifetimes of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) were d
etermined in a large number of solvents and solvent mixtures, displaying va
riations from 825 ns in CD3CN to 13 ns in CHCl3. Large deuterium isotope ef
fects (8-11) and significant activation energies (generally 2-15 kJ mol(-1)
) for fluorescence quenching of DBO are observed, which support a novel sol
vent-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.