Mixed Valency Systems

Mixed valency is one of various names used to describe compounds which contain ions of the same element in two different formal states of oxidation. The existence of mixed valency systems goes far back into the geological evolutionary history of the earth and other planets, while a plethora of mixed valency minerals has attracted attention since antiquity. Indeed, control of the oxidation states of Fe in its oxides (FeO, Fe304' Fe203) was elegantly used in vase painting by the ancient Greeks to produce the characteristic black and red Attic ceramics (Z. Goffer, "Archaeological Chemistry", Wiley, New York, 1980). It was, however, only 25 years ago that two reviews of mixed valency appeared in the literature almost simultaneously, signalling the first attempt to treat mixed valency systems as a separate class of compounds whose properties can be correlated with the molecular and the electronic structure of their members. Then mixed valency phenomena attracted the interest of disparate classes of scientists, ranging from synthetic chemists to solid state physicists and from biologists to geologists. This activity culminated with the NATO ASI meeting in Oxford in 1979. The 1980's saw again a continuing upsurge of interest in mixed valency. Its presence is a necessary factor in the search for highly conducting materials, including molecular metals and superconductors. The highly celebrated high T c ceramic superconducting oxides are indeed mixed valency compounds.