The solvent dependence of the intervalence transition (IT) band of the very weakly coupled binuclear (2,8-dithiadispiro-[22.214.171.124]decane)decaamminediruthenium(II,III) hexafluorophosphate was studied. No correlation could be discerned with any solvent parameter. A dependence of the optical band of the ruthenium binuclear complex, Eop, on the ionic strength of the medium was observed, with some solvents showing stronger effects than others. When ionic strength studies were performed and the extrapolated values at zero ionic strength were employed, a correlation of Eop0 with 1/Dop - 1/Ds was observed. The calculated inner-sphere reorganizational energy, λi, was 25 kcal/mol. The calculated slope of the plot of Eop0 against 1/Dop - 1/Ds was 20.7 whereas the measured value was only 2.02. These results indicate that the dielectric continuum model is not appropriate for theories used in analyzing IT bands of very weakly coupled mixed-valence complexes.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry