Abstract
A study of the metal-to-metal charge-transfer (MMCT) transition within the binuclear cyano-bridged complexes cis-[L 13Co III(μ-NC)Fe II(CN) 5] − (L 13 = 12-methyl-1,4,7,10-tetraazacyclotridecan-12-amine), trans-[L 14Co III(μ-NC)Fe II(CN) 5] − (L 14 = 6-methyl-1,4,8,11-tetraazacyclotetradecan-6-amine) and trans-[L 15Co III(μ-NC)Fe II(CN) 5] − (L 15 = 10-methyl-1,4,8,12-tetraazacyclopentadecan-10-amine) has been carried out in electrolyte solutions at varying concentrations. Using these data, as well as the reaction free energies obtained from electrochemical measurements, the reorganisation and activation free energies for the forward and reverse thermal electron-transfer processes have been estimated. The changes of these parameters with the electrolyte concentration, as well as those of the energy of the maximum MMCT band and the reaction free energy, are mainly due to ion-pairing effects.
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