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AIC405166'The oxidation state properties of the compounds biferrocene, 1 ,I '-terferrocene, and 1,l'-quaterferrocene have been investigated using electrochemical techniques. In the polymeric compounds all of the ferrocene groups are oxidizable to ferricenium at distinct potentials. The values of the potentials can be predicted in some cases using ferrocenyl substituent effects. Partial oxidation gives a series of discrete mixed-valence ions. The mixed-valence ions can exist as a series of oxidation state isomers which differ with regard to the site of oxidation. Electron transfer between different oxidation state sites in the polymeric chains is unsyinmetric giving energetically nonequivalent isomers. The unsymmetrical nature of electron transfer is reflected in the properties of intervalence-transfer (IT) absorptions in the near-infrared spectra. The existence of energetically equivalent and nonequivalent oxidation state isomers may also influence such properties as the intensities of I T bands, the presence of statistical effects in measured reduction potentials, and rates of intramolecular electron transfer.

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