Uranium pyrophosphate/methylenediphosphonate polyoxometalate cage clusters.

Despite potential applications in advanced nuclear energy systems, nanoscale control of uranium materials is in its infancy. In its hexavalent state, U occurs as (UO(2))(2+) uranyl ions that are coordinated by various ligands to give square, pentagonal, or hexagonal bipyramids. Creation and design of nanostructured uranyl materials requires interruption of the tendency of uranyl bipyramids to share equatorial edges to form infinite sheets that occur in extended structures. Where a bidentate peroxide group bridges uranyl bipyramids, the configuration is inherently bent, fostering formation of cage clusters. Here the bent configurations of four- and five-membered rings of uranyl peroxide hexagonal bipyramids are bridged by pyrophosphate or methylenediphosphonate, creating eight chemically complex cage clusters with specific topologies. Chemical complexity in such clusters provides opportunities for the tuning of cage sizes, pore sizes, and properties such as aqueous solubility. Several of these are topological derivatives of simpler clusters that contain only uranyl bipyramids, whereas others exhibit new topologies.