Ce Oxosulfate Rings, Frameworks, Supramolecular Assembly, and Redox Activity*.

M 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 , a wheel-shaped oxo-cluster, [Ce (OH) (O) (SO ) (H O) ] . Ce 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 -rings are linked as propellers, in offset-stacks, in a tartan pattern, and as isolated rings. Small-angle X-ray scattering of Ce dissolved in butylamine, with and without added cations (Ce , alkaline earths, Mn ), 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 and Nd . Frameworks featuring Ce -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.