Four metal-organic frameworks (MOF) with tetravalent uranium have been solvothermally synthesized by treating UCl4 with rigid dicarboxylate linkers in N,N-dimethylfomamide (DMF). The use of the ditopic ligands 4,4'-biphenyldicarboxylate (1), 2,6-naphthalenedicarboxylate (2), terephthalate (3), and fumarate (4) resulted in the formation of three-dimensional networks based on the hexanuclear uranium-centered motif [U6O4(OH)4(H2O)6]. This motif corresponds to an octahedral configuration of uranium nodes and is also known for thorium in crystalline solids. The atomic arrangement of this specific building unit with organic linkers is similar to that found in the zirconium-based porous compounds of the UiO-66/67 series. The structure of [U6O4(OH)4(H2O)6(L)6]⋅X (L = dicarboxylate ligand; X = DMF) shows the inorganic hexamers connected in a face-centered cubic manner through the ditopic linkers to build up a three-dimensional framework that delimits octahedral (from 5.4 Å for 4 up to 14.0 Å for 1) and tetrahedral cavities. The four compounds have been characterized by using single-crystal X-ray diffraction analysis (or powder diffraction analysis for 4). The tetravalent state of uranium has been examined by using XPS and solid-state UV/Vis analyses. The measurement of the Brunauer-Emmett-Teller surface area indicated very low values (Langmuir <300 m(2)  g(-1) for 1, <7 m(2)  g(-1) for 2-4) and showed that the structures are quite unstable upon removal of the encapsulated DMF solvent.

By controlling the water content, a new poly-oxo-metalate species containing 38 uranium centers has been solvothermally synthesized in the presence of benzoic acid in tetrahydrofuran (THF). The {U38} motif contains a distorted UO2 core of fluorite type, stabilized by benzoate and THF molecules. This compound is analogous to the {Pu38} motif and was characterized by X-ray photoelectron spectroscopy and magnetic analyses.