The first study of the effect of pressure on the intervalence transfer (IT) band of a very weakly coupled mixed valence binuclear, (μ-2,6-dithiaspiro[3.3]heptane)decaamminediruthenium(II,III) hexafluorophosphate in D2O is reported. A red shift of more than 200 cm-1 and a small increase in the oscillator strength of the IT band were observed over a pressure range of 1500 bars. These effects were interpreted as arising primarily from H-bonding between the ammine groups on the ruthenium atoms and the solvent D2O molecules. A nonadiabatic, multiphonon electron-tunnelling theory was employed to calculate rates of thermal electron transfer at each pressure, and ΔV‡ was estimated to be -7.5 ± 0.2 cm3/mol for the thermal electron exchange.
ASJC Scopus subject areas
- Colloid and Surface Chemistry