Structure and Solution Speciation of UIV Linked Phosphomolybdate (MoV) Clusters

Crystals of [NaU(Mo6P4O31H7)2]·5Na·(H2O)n (NaUMo6) have been synthesized by slow evaporation of an aqueous mixture containing uranyl nitrate, sodium molybdate, phosphoric acid, and sodium dithionate. Single crystal diffraction of NaUMo6 reveals the assembly of {Mo6P4} clusters linked into one-dimensional chains with alternating Na(+) and U(4+) cations. To our knowledge, NaUMo6 is a unique example of Mo(5+) based polyoxometalate associated with actinides. With the use of similar synthesis conditions but without uranium in the aqueous solution, [Na(Mo6P4O31H10)2]·5Na·(H2PO4)·(H2O)n (NaMo6) is obtained. NaMo6 is a sandwich type cluster which is built on the assemblage of two {Mo6P4} units linked by one sodium cation. Using small-angle X-ray scattering techniques and aqueous electrolyte based dissolution strategies, we can accurately observe chains of [UNa(Mo6P4O31H7)2]n(5n), where n = 7 is the dominant soluble specie. Likewise, the dimeric form of [Na(Mo6P4O31H10)2](5-) dominates the aqueous solution, revealing the structural units observed in the crystal structure are also stable in solution, under appropriate dissolution conditions.