Supramolecular Assembly of U(IV) Clusters and Superatoms

Abstract

Superatoms are nanometer-sized molecules or particles that can form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in superlattices of quantum-dots, p-block clusters, and fullerenes. Here, we introduce a family of uranium-oxysulfate cluster anions whose hierarchical assembly in water is controlled by two parameters; acidity and the countercation. In acid, larger Ln<sup>III</sup> (Ln=La-Ho) link hexamer (U<sub>6</sub>) oxoclusters into body-centered cubic frameworks, while smaller Ln<sup>III</sup> (Ln=Er-Lu &Y) promote linking of fourteen U<sub>6</sub>-clusters into hollow superclusters (U<sub>84</sub> superatoms). U<sub>84</sub> assembles into superlattices including cubic-closest packed, body-centered cubic, and interpenetrating networks, bridged by interstitial countercations, and U<sub>6</sub>-clusters. Divalent transition metals (TM=Mn<sup>II </sup>and Zn<sup>II</sup>), with no added acid, charge-balance and promote the fusion of 10 U<sub>6</sub> and 10 U-monomers into a wheel–shaped cluster (U<sub>70</sub>). Dissolution of U<sub>70</sub> in organic media reveals (by small-angle Xray scattering) that differing supramolecular assemblies are accessed, controlled by TM-linking of U<sub>70</sub>-clusters. <br>