CeIV70 Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity**

M-IV molecular oxo-clusters (M=Zr, Hf, Ce, Th, U, Np, Pu) are prolific in bottoms-up material design, catalysis, and elucidating reaction pathways in nature and in synthesis. Here we introduce Ce-70, a wheel-shaped oxo-cluster, [Ce-70(IV)(OH)(36)(O)(64)(SO4)(60)(H2O)(10)](4-). Ce-70 crystallizes into intricate high pore volume frameworks with divalent transition metals and Ce-monomer linkers. Eight crystal-structures feature four framework types in which the Ce-70-rings are linked as propellers, in offset-stacks, in a tartan pattern, and as isolated rings. Small-angle X-ray scattering of Ce-70 dissolved in butylamine, with and without added cations (Ce-IV, alkaline earths, Mn-II), shows the metals' differentiating roles in ring linking, leading to supramolecular assemblies. The large acidic pores and abundant terminal sulfates provide ion-exchange behavior, demonstrated with U-IV and Nd-III. Frameworks featuring Ce-III/IV-monomer linkers demonstrate both oxidation and reduction. This study opens the door to mixed-metal, highly porous framework catalysts, and new clusters for metal-organic framework design

Automated summary

M-IV molecular oxo-clusters, such as Ce-70, have diverse crystal structures and can form intricate frameworks with divalent transition metals and Ce-monomer linkers. These clusters show potential for catalysis, ion exchange, and oxidation-reduction reactions, opening up new possibilities for metal-organic framework design.