Journal of Physical Chemistry A, Vol.101, No.9, 1689-1695, 1997
Unusual Size Dependence of Nonradiative Charge Recombination Rates in Acetylene-Bridged Compounds
Time-resolved fluorescence decays of three asymmetrically substituted phenylethynyl molecules of different size show a sizable solvent dependence. Nonradiative rate constants estimated from quantum yield and lifetime data are consistent with classical electron-transfer theory. The electronic coupling elements, H-RP, derived from fits of theory to the data do not follow the trend of donor-acceptor distance (or molecular size). It is found to be largest for the molecule with a butadiyne linker which is intermediate in size. Our results suggest that the bridge is directly involved in excited-state charge recombination in these conjugated molecules.
Keywords:PHOTOINDUCED ELECTRON-TRANSFER;EXCITED SINGLET-STATE;ENERGY-GAP LAW;DIPHENYLACETYLENE;MOLECULES;SPECTRA;DECAY;TOLAN