Supramolecular Assembly of CeIV-Oxo Sulfate Torus with Transition Metal Countercations

Abstract

M<sup>IV</sup> molecular oxo-clusters of the <i>f-</i> and <i>d</i>-block (M=Zr, Hf, Ce, Th, U, Np, Pu) have been prolific in bottoms-up material design, catalysis, as well as understanding metal oxide assembly, dissolution and surface reactivity in nature and in synthesis. Here we introduce Ce<sub>70</sub>, a new Ce<sup>IV</sup> wheel-shaped oxo-cluster, [Ce<sup>IV</sup>(OH)<sub>36</sub>(O)<sub>64</sub>(SO<sub>4</sub>)<sub>60</sub>(H<sub>2</sub>O)<sub>10</sub>]<sup>4-</sup>, isostructural with prior-reported U<sub>70</sub>. Like U<sub>70</sub>, Ce<sub>70</sub> crystallizes into intricate frameworks with divalent transition metal counter-cations (TM<sup>II</sup>), and also Ce<sup>IV</sup>-monomer and sulfate addenda ions.