Abstract
The temperature dependencies of the quenching rate constants (kq) and cage escape yields of the redox products (ηce) from the electron-transfer reaction of *Ru(bpy)32+ (bpy = 2,2‘-bipyridine) with nine aromatic amines in deaerated 1:1 (v/v) CH3CN/H2O solutions have been determined. Values of λ, the solvent reorganization energy for electron-transfer quenching and back electron transfer within the solvent cage, have been extracted from plots of log(kqT1/2) vs 1/T and log((ηce-1 − 1)T1/2) vs 1/T, respectively. For the quenching process, λ is not a constant value for the series of quenchers; in general, higher values of λ are exhibited by primary amines and lower values by tertiary amines. The structure and size of the quenchers and the nature of the ring substituents contribute to the value of λ. For the back-electron-transfer reaction within the geminate redox pair formed in the quenching process, the more sterically hindered two-ring amines exhibit a higher value of λ (1.1 ± 0.08 eV) than do the majority ...
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