Abstract
The synthesis and characterization of a series of (TBA)(2)[M{Mo(5)O(13)(OMe)(4)NO}(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 {Mo(5)} 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{Mo(5)O(13)(OMe)(4)NO}(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.