ABSTRACT
The synthesis and characterization of a series of (TBA)2[M{Mo5O13(OMe)4NO}2] (M = Zr, Hf, Th, and U) sandwich complexes is reported. A preformed lacunary, Lindqvist-type, polyoxomolybdate-alkoxide cluster provides access to first examples of actinide-polyoxomolybdate sandwich complexes isolated under non-aqueous conditions. Incorporation of metal(iv) cations into this framework was found to "switch on" reversible redox chemistry at the {Mo5} ligands, with the Zr and Hf containing complexes accepting up to two electrons, while the Th and U derivates accommodate as many as four additional electrons. The enhancement of the redox properties of the cluster upon actinide incorporation is an exciting observation, presenting actinide "doping" as a novel approach for accessing functional redox-active materials. Oxidation of the uranium containing sandwich complex (TBA)2[U{Mo5O13(OMe)4NO}2], chemically or electrochemically, allows access to the U(v) centered species, which was characterized both spectroscopically and by single crystal X-ray diffraction. This represents the first example of a U(v)-polyoxometalate sandwich complex to be isolated and structurally characterized.
ABSTRACT
A new isopolyoxotungstate has been characterised, thirty years since the first spectroscopic evidence of its existence. The heptatungstate [W7O24H]5-, containing a {W5} lacunary Lindqvist unit fused to a ditungstate fragment, has significant stability and is only the third isopolytungstate structure to be obtained from non-aqueous systems.
