Implications of the unusual redox behavior exhibited by the heteropolyanion [EuP{sub 5}W{sub 30}O{sub 110}]{sup 12{minus}}

Materials containing more than one electroactive species may exhibit a variety of unusual properties, including mixed or intermediate valence, and their related phenomena. Intermediate valence arises when localized orbitals, notably valence f-states, interact in a bonding fashion with delocalized, molecular orbitals in the same material. Electrons are viewed to be rapidly hopping between these two very different kinds of orbitals, and it is their relative residence times that are interpreted as a non-integral valence. Whereas there has been considerable efforts expended to understand this unusual behavior, these efforts have not proven successful, largely because the problem is many-bodied and is usually studied on infinite band states, often in chemically complex systems. The authors report here on the novel electrochemical behavior of the heteropolyanion [EuP{sub 5}W{sub 30}O{sub 110}]{sup 12}, and examine the valence of Eu in both the oxidized and reduced form of the anion, as determined from Eu L{sub 3}-edge X-ray absorption near edge structure (XANES). The results demonstrate that, with careful electrochemical control, Eu in this ion may become intermediate valent. Such a result would provide an entirely new and unique approach to longstanding questions related to the phenomenon of intermediate valence