Metal-Oxo Cluster Formation Using Ammonium and Sulfate to Differentiate M^IV (Th, U, Ce) Chemistries

Isolating isostructural compounds of tetravalent metals M^IV (Zr, Hf, Ce, Th, U, Pu, Np) improves our understanding of metal hydrolysis and coordination behavior across the periodic table. These metals form polynuclear clusters typified by the hexamer [M^IV₆O₄(OH)₄]¹²⁺. Exploiting the ammonium M^IV-sulfate (Ce^IV, Th^IV, and U^IV) phase space targeting rapid crystallization, we isolate the common hexamer [M^IV₆(OH)₄(O)₄]¹²⁺ but with different numbers of capping sulfates and water molecules for Ce^IV, Th^IV, and U^IV. These phases allowed a direct comparison of bonding trends across the series. Upon cocrystallization with the hexamers, higher complex structures can be identified. Thorium features assemblies with monomer-linked hexamer chains. Uranium features assemblies with sulfate-bridged hexamers and the supramolecular assembly of 14 hexamers into the U₈₄, [U₆(OH)₄(O)₄)₁₄(SO₄)₁₂₀(H₂O)₄₂]^72-. Last, cerium showcases the isolation from monomers to the Ce₆₂, [Ce₆₂(OH)₃₀(O)₅₈(SO₄)₇₁(H₂O)_33.25]^41-. Furthermore, small-angle X-ray scattering (room temperature) shows ammonium-induced cluster assembly for Ce^IV but minimal reactivity for U^IV and Th^IV. In this study, because the phases crystallized at elevated temperature demonstrates favorable cluster assembly, these solution phase results were surprising and suggest some other characteristics such as Ce's facile redox behavior, contributes to its solution-phase speciation.