Tetravalent Uranium Research Articles

Valence Stabilization of Polyvalent Uranium Ions in Presence of Some Organic Additives during Extended Gamma Irradiation of Their Aqueous Acidic Solutions

In gamma irradiated aqueous acidic uranium solutions, tetravalent uranium ions are easily oxidized while U(VI) ions remain unchanged. In general, valence change of polyvalent metallic ions during chemical reprocessing of spent nuclear fuel solutions can lead to undesirable effects under the influence of the existing gamma radiations. Consequently, studies on valence stabilization of Uranium ions during chemical treatment in strong gamma irradiation fields seem to be highly interesting. It has been reported before that some organic compounds proved to be effective in stabilizing the valence of Fe(II) ions during extended gamma irradiation of their acidic solutions. In the present work, valence stabilization of Uranium ions in acidic solutions in presence of different classes of organic compounds has been studied. The results showed that in case of U(IV), methanol or formic acid are capable of providing about 80% protection while ethanol or acetaldehyde can provide about 70% protection. Propanol has the least protective effect i.e. about 54%. On using U(VI) instead of U(IV) in the irradiated solutions, the uranium ions were reduced and the formed U(IV) was protected as follows: formic acid or methanol can provide 69% or 63% protection respectively while ethanol, acetaldehyde or propanol can provide 50%, 35% and 24% respectively. In any case, protection exists as long as the organic additives were not completely consumed.

Coordination polymers of uranium(IV) terephthalates.

A series of tetravalent uranium terephthalates has been solvothermally synthesized in the solvent N,N-dimethylformamide (DMF) at temperature 100-150 °C with different water amounts. Composition diagrams have been determined for the U(4+) metallic cation in the presence of terephthalic acid, and their crystal structures revealed the occurrence of two- or three-dimensional coordination polymers. In the absence of water, a mixture of two polytypes T-U(2)Cl(2)(bdc)(3)(DMF)(4) (1) and M-U(2)Cl(2)(bdc)(3)(DMF)(4) (2) has been identified at low temperature (100-110 °C) for bdc/U = 1-4 (bdc = terephthalate linker). Their structures are built up from isolated uranium centers in nine-fold coordination, surrounded by 6 carboxyl oxygen atoms, 2 oxygen atoms coming from DMF molecules and one chlorine atom. The uranium cations are linked to each other through the bdc ligand in order to generate a 3D framework. By increasing the temperature (130-150 °C), a layered like compound has been isolated, U(2)(bdc)(4)(DMF)(4) (3). It is composed of discrete actinide centers in ten-fold coordination, with 8 carboxyl oxygen atoms and 2 oxygen atoms from DMF molecules. The connection of the UO10 units with the bdc linkers generates 2D sheets. When a controlled amount of water is added to the reaction medium, the crystallization of the UiO-66-like U(6)O(4)(OH)(4)(H(2)O)(6)(bdc)(6)·10DMF solid (containing a hexanuclear sub-unit) is observed for temperature 110-120 °C and the H(2)O/U molar ratio in the range of 2-10. At higher temperature (140-150 °C), a distinct phase appeared, U(2)O(2)(bdc)(2)(DMF) (4), which consists of infinite chains of uranium centers, linked to each other via the bdc ligands. Higher water contents led to the formation of urania UO(2).

Isotope fractionation during oxidation of tetravalent uranium by dissolved oxygen

We conducted laboratory experiments to investigate isotopic fractionations during oxidation of tetravalent uranium, U(IV), by dissolved oxygen. In hydrochloric acid media with the U(IV) dissolved, the δ238U value of the remaining U(IV) increased as the extent of oxidation increased. The δ238U value of the product U(VI) paralleled, but was offset to 1.1±0.2‰ lower than the remaining U(IV). In contrast, oxidation of solid U(IV) by dissolved oxygen in 20mM NaHCO3 solution at pH=9.4 caused only a weak fractionation (∼0.1‰ to 0.3‰), with δ238U being higher in the dissolved U(VI) relative to the solid U(IV). We suggest that isotope fractionation during oxidation of solid U(IV) is inhibited by a “rind effect”, where the surface layer of the solid U(IV) must be completely oxidized before the next layer is exposed to oxidant. The necessity of complete conversion of each layer results in minimal isotopic effect. The weak shift in δ238U of U(VI) is attributed to adsorption of part of the product U(VI) to the solid U(IV) surfaces.

Dissolution of Th1−xUxO2: Effects of chemical composition and microstructure

The dissolution of Th1−xUxO2 solid solutions was studied by varying independently several parameters such as chemical composition, leachate acidity, leaching temperature, firing temperature, and densification state. The chemical durability of the samples was significantly affected by the uranium mole loading probably due to the oxidation of tetravalent uranium into uranyl during the dissolution process. The influence of nitric acid concentration and temperature also showed that the behavior of Th1−xUxO2 solid solutions with higher uranium incorporation fractions (x=0.52, 0.75 and 1) differed significantly from that of Th0.84U0.16O2. Strong modifications of the dissolution mechanism occurring at the solid/liquid interface for the higher uranium loadings could explain this difference. It could result in the existence of the fast oxidation of U(IV) to U(VI) at the solid/solution interface then of the detachment of activated complexes formed with U(VI). Furthermore, initial normalized dissolution rate slightly depended on the elimination of crystal defects for firing temperatures below 900°C but was almost independent of the crystallite size (T⩾900°C). Finally, dissolution tests on sintered Th0.84U0.16O2 samples showed that RL(Th) values decreased by an order of magnitude when the relative density increased from 79% to 89%.

Solid-state syntheses and single-crystal characterizations of three tetravalent thorium and uranium silicates

Colorless crystals of ThSiO4 (huttonite) (1) and (Ca0.5Na0.5)2NaThSi8O20 (2) have been synthesized by the solid-state reactions of ThO2, CaSiO3, and Na2WO4 at 1073K. Green crystals of (Ca0.5Na0.5)2NaUSi8O20 (3) have been synthesized by the solid-state reactions of UO2, CaSiO3, and Na2WO4 at 1003K. All three compounds have been characterized by single-crystal X-ray diffraction. Compound 1 adopts a monazite-type three-dimensional condensed structure, which is built from edge- and corner-shared ThO9 polyhedra and SiO4 tetrahedra. Compounds 2 and 3 are isostructural and they crystallize in a steacyite-type structure. The structure consists of discrete pseudocubic [Si8O20]8− polyanions, which are connected by An4+ cations into a three-dimensional framework. Each An atom coordinates to eight monodentate [Si8O20]8− moieties in a square antiprismatic geometry. Na+ and Ca2+ ions reside in the void within the framework. Raman spectra of 1, 2, and 3 were collected on single crystal samples. 1 displays more complex vibrational bands than thorite. Raman spectra of 2 and 3 are analogous with most of vibrational bands located at almost the same regions.

Optical properties of tetravalent uranium complexes in non-aqueous media

We study photo-physical behaviors of tetravalent uranium halides such as UF4, UCl4, UBr4 and UI4 to understand the electronic transitions under the unexplored condition such as in non-aqueous media at cryogenic temperature. These complexes exhibit white fluorescence by UV-pulse excitation at λex = 394 nm. The fluorescence lifetimes in organic solvents are shorter than that in ionic liquids in spite of the longer ionic radii between uranium and ligands. Chemical species and the coordination number of UIV in water, in organic solutions, and in ionic liquids are thoroughly different, resulting in a variety of fluorescence spectra and decays.

ChemInform Abstract: The Crystal Chemistry of Uranium Carboxylates

AbstractReview: 345 refs.

Phosphosilicates of tetravalent uranium

A new variety of P-coffinite of (U,Ca,Fe)[(Si,P,S)O4] idealized formula where P and C are the mineral-forming elements equally to U and Si has been discovered. This allows one to enlarge the list of the known minerals of tetravalent uranium with a new mineral taxon of U4+ phosphosilicates. The crystalline structure of phosphosilicates is difficult to solve because of the dispersity of μm-sized crystals; therefore, crystallochemical analysis of probable transformations of mineral structures in polyhedrons was carried out. The consideration of the structures from coffinite (U4+-silicate) to ningyoite (Ca-U4+-phosphate) resulted in the conclusion on the possible existence of a series of U4+ minerals of mixed anionic and, hence, cationic composition, i.e., of phosphosilicates and silicophosphates of tetravalent uranium, with the indispensable presence of calcium in the crystalline structure.

ChemInform Abstract: Crystal Structures of Tetravalent Uranium Fluorides Obtained in the Presence of Hydrazine from Uranyl Source.

AbstractThe crystal structures of the tetravalent uranium fluorides (V), (VI), (IX), and (X), which could not be prepared as single phases, are determined by single crystal XRD.

Probing Uranium(IV) Hydrolyzed Colloids and Polymers by Light Scattering

Tetravalent uranium readily undergoes hydrolysis even in highly acidic aqueous solutions. In the present work, solutions ranging from 0.4 to 19 mM (total U) concentration (1<pH<4) are carefully investigated by light scattering technique with special emphasis on polymerization leading to colloid formation. The results clearly indicate that the concentration has significant effect on particle size as well as stability of colloids. With increasing concentration the size of colloids formed is smaller due to more crystalline nature of the colloids. Stability of colloids formed at lower concentration is greater than that of colloids formed at higher concentration. Weight average molecular weight of the freshly prepared and colloidal polymers aged for 3 days is determined from the Debye plot. It increases from 1,800 to 13,000 Da. 40–50 atoms of U are considered to be present in the polymer. Positive value of second virial coefficient shows that solute-solvent interaction is high leading to stable suspension. The results of this work are a clear indication that U(IV) hydrolysis does not differ from hydrolysis of Pu(IV).

Crystal structures of tetravalent uranium fluorides obtained in the presence of hydrazine from uranyl source

Four new tetravalent uranium fluorides have been obtained by using hydrothermal route from a hexavalent uranium precursor (UO2(NO3)2·6H2O or UO2(SO4)·4H2O) in the presence of hydrazine and HF in water. The major phase is the hydrated uranium fluoride U3F12(H2O) (1) and in some conditions, four other phases are formed in mixture with the latter. Both compounds 2 and 3 exhibit layered structures with intercalated hydrazinium cations. UF5·H3N-NH2 (2) consists of double uranium fluoride sheets with nine-fold coordinated uranium (UF9, tricapped trigonal prism). It is related to the anionic archetype [UF5]−·X+ or [U2F10]2−·Y2+ (depending of the charge of the counter-cations) previously reported in literature. U3F4(SO4)6·2NH4·H3N-NH3 (3) contains trinuclear μ3-fluoro-centered uranium (UO6F3, tricapped trigonal prism) core linked to each other via the sulfate groups in order to form infinite sheets intercalated by ammonium and diprotonated hydrazinium cationic species. It is a new type of uranium arrangement for tetravalent uranium sulfates. The phases NaU2F9 (4) and NaU6F25 (5) appeared when sodium sulfate is added to the reaction medium. Crystal structure of 4 can be viewed from the connection of double uranium fluorides layers of nine-fold coordinated uranium (UF9) centers, similar to that observed in the compound 2. Due to the small size of sodium cation, the resulting [UF5]− sheets are connected to each other via the remaining non-bonded fluoride anions in order to form a three-dimensional network with channels encapsulating the alkali atoms. The structure of NaU6F25 (5) corresponds to the stacking of double layers of 6-membered ring sub-net of UF9 units, resulting in the formation of elongated cavities in which sodium atoms are located.

Mobile uranium(IV)-bearing colloids in a mining-impacted wetland

Tetravalent uranium is commonly assumed to form insoluble species, resulting in the immobilization of uranium under reducing conditions. Here we present the first report of mobile U(IV)-bearing colloids in the environment, bringing into question this common assumption. We investigate the mobility of uranium in a mining-impacted wetland in France harbouring uranium concentrations of up to 14,000 p.p.m. As an apparent release of uranium into the stream passing through the wetland was observable, we examine soil and porewater composition as a function of depth to assess the geochemical conditions leading to this release. The analyses show the presence of U(IV) in soil as a non-crystalline species bound to amorphous Al-P-Fe-Si aggregates, and in porewater, as a distinct species associated with Fe and organic matter colloids. These results demonstrate the lability of U(IV) in these soils and its association with mobile porewater colloids that are ultimately released into surface water.

Vorlanite, (CaU6+)O4, from Jabel Harmun, Palestinian Autonomy, Israel

Vorlanite (CaU 6+ )O 4 [ Fm 3 m , a = 5.3647(9) A, V = 154.40(4) A 3 , Z = 2] was found in larnite pyrometamorphic rocks of the Hatrurim formation at the Jabel Harmun locality, Judean Desert, Palestinian Autonomy. Vorlanite crystals from these larnite rocks are dark-gray with greenish hue in transmitted light. This color in transmitted light is in contrast to dark-red vorlanite [ Fm 3 m , a = 5.3813(2) A, V = 155.834(10)A 3 , Z = 2] from the type locality Upper Chegem caldera, Northern Caucasus. Heating above 750 °C of dark-gray vorlanite from the Jabel Harmun, as well as dark-red vorlanite from Caucasus, led to formation of yellow trigonal uranate CaUO 4 . The unusual color of vorlanite from Jabel Harmun is assumed to be related to small impurities of tetravalent uranium.

Comprehensive Uranium Thiophosphate Chemistry: Framework Compounds Based on Pseudotetrahedrally Coordinated Central Metal Atoms

AbstractThe new ternary compounds UP2S6, UP2S7, U(P2S6)2, and U3(PS4)4 were prepared from uranium metal, phosphorus pentasulfide, and sulfur at 700 °C. The crystal structures were determined by single‐crystal X‐ray diffraction methods. UP2S6 (I) crystallizes in the ZrP2S6 structure type [tetragonal, P42/m, a = 6.8058(7) Å, c = 9.7597(14) Å, Z = 2], which consists of central uranium(IV) atoms coordinated by P2S64– anions (staggered conformation). The anions are two‐dimensional connectors for four uranium cations arranged in one plane. The structure of UP2S7 (II) [orthorhombic, Fddd, a = 8.9966(15) Å, b = 15.2869(2) Å, c = 30.3195(5) Å, Z = 16] is closely related to the monoclinic ZrP2S7 structure type. It consists of U4+ cations linked by P2S74– ligands, the resulting 3D network contains large pores (diameter approx. 3.5 × 16.7 Å). In the previously reported compound U(P2S6)2 (III) [I41/a, a = 12.8776(9) Å, c = 9.8367(10) Å, Z = 2], the metal atoms are coordinated by four bidentate P2S62– ligands. This arrangement can be considered as a pseudotetrahedral coordination of the uranium atoms by the linear ligands. Three of the resulting diamondoid frameworks are inseparably interwoven in order to optimize space filling. U3(PS4)4 (IV) [I41/acd, a = 10.7440(9) Å, c = 19.0969(2) Å, Z = 2] crystallizes in a defect variant of the PrPS4 structure type, with 50 % of the U2 sites statistically occupied with uranium atoms. The resulting stoichiometry is U3(PS4)4 with tetravalent uranium atoms. The structure of U3(PS4)4 consists of uranium atoms connected by PS43– groups, each PS4 group linking four central uranium atoms. Vibrational spectra, which were recorded for I–III, show good agreement between the obtained results and the expected values for the anionic units, while magnetic measurements confirm the presence of tetravalent uranium.

Mixed Formate-Dicarboxylate Coordination Polymers with Tetravalent Uranium: Occurrence of Tetranuclear {U4O4} and Hexanuclear {U6O4(OH)4} Motifs

Two new three-dimensional coordination networks with tetravalent uranium have been solvothermally synthesized by associating UCl4 and a combination of two carboxylate-based ligands in N,N-dimethylformamide (DMF). The mixture of terephthalate (bdc) and formate (form) resulted in the formation MOF-type structure (Hdma)[U4O2(bdc)3(form)7] based on the tetranuclear uranium-centered motif {U4O4}. This inorganic building block is relatively rare in the actinides chemistry and generates here a negatively charged framework trapping dimethylammonium cations resulting from the in situ decomposition of DMF. The association of formate (form) and fumarate (fum) led to the isolation of the hexameric building block {U6O4(OH)4} in a three-dimensional framework (U6O4(OH)4(fum)5(form)2(H2O)2·3DMF) closely related to the topology observed with single ditopic ligand in the UiO-66 series. The porous solid contained two types of cages with estimated free pore diameters of 6.3 × 6.7 A and 4.7 A.

Thermodynamics of Tetravalent Thorium and Uranium Complexes from First-Principles Calculations

Enthalpies of formation for the ThX4 and UX4 (X = F, Cl, OH) species have been investigated with density functional theory and coupled-cluster methods. ThX4 molecules are all confirmed as tetrahedral, while all UX4 molecules are predicted to adopt D2d symmetry using density functional theory. Multireference coupled cluster approaches confirm the D2d symmetry for UF4. The bonding is mostly ionic, and predicted formation energies for the halogen species show good agreement with experiment. Our calculated hydration energy of UF4 (-54.0 kcal/mol) is in very good agreement with the experimental data (-54.8 kcal/mol). We predict CCSD(T) formation energies of ΔfG[U(OH)4(g)] = -286.3 kcal/mol and ΔfG[U(OH)4(aq)] = -318.7 kcal/mol. ΔfG[U(OH)4(aq)] is 21 kcal/mol less stable than the established experimental thermodynamic data.

Reaction of UVI with Titanium-Substituted Magnetite: Influence of Ti on UIV Speciation

Reduction of hexavalent uranium (U(VI)) to less soluble tetravalent uranium (U(IV)) through enzymatic or abiotic redox reactions has the potential to alter U mobility in subsurface environments. As a ubiquitous natural mineral, magnetite (Fe3O4) is of interest because of its ability to act as a rechargeable reductant for U(VI). Natural magnetites are often impure with titanium, and structural Fe(3+) replacement by Ti(IV) yields a proportional increase in the relative Fe(2+) content in the metal sublattice to maintain bulk charge neutrality. In the absence of oxidation, the Ti content sets the initial bulk Fe(2+)/Fe(3+) ratio (R). Here, we demonstrate that Ti-doped magnetites (Fe3-xTixO4) reduce U(VI) to U(IV). The U(VI)-Fe(2+) redox reactivity was found to be controlled directly by R but was otherwise independent of Ti content (xTi). However, in contrast to previous studies with pure magnetite where U(VI) was reduced to nanocrystalline uraninite (UO2), the presence of structural Ti (xTi = 0.25-0.53) results in the formation of U(IV) species that lack the bidentate U-O2-U bridges of uraninite. Extended X-ray absorption fine structure spectroscopic analysis indicated that the titanomagnetite-bound U(IV) phase has a novel U(IV)-Ti binding geometry different from the coordination of U(IV) in the mineral brannerite (U(IV)Ti2O6). The observed U(IV)-Ti coordination at a distance of 3.43 Å suggests a binuclear corner-sharing adsorption/incorporation U(IV) complex with the solid phase. Furthermore, we explored the effect of oxidation (decreasing R) and solids-to-solution ratio on the reduced U(IV) phase. The formation of the non-uraninite U(IV)-Ti phase appears to be controlled by availability of surface Ti sites rather than R. Our work highlights a previously unrecognized role of Ti in the environmental chemistry of U(IV) and suggests that further work to characterize the long-term stability of U(IV) phases formed in the presence of Ti is warranted.

Trace and REE element geochemistry of fluorite and its relation to uranium mineralizations, Gabal Gattar Area, Northern Eastern Desert, Egypt

Uranium mineralizations occur and form in a broad range of geologic setting and age, including magmatic to surfacial conditions, and there are numerous controls on their transportation and deposition, such as redox, pH, ligand concentration, complexation, and temperature. These temporal and spatial variations have caused a range of ore deposit mineral assemblages. Consequently, understanding their conditions of formation is still in its infancy. This research reports rare earth elements (REE) and trace elements of fluorite associated with hexavalent uranium mineralizations and tests of genetic models for the deposits. These data contribute to a better understanding of the variables controlling fluorite formation and uranium ore composition through understanding the evolution of these ore-forming hydrothermal systems. Fluorite in Gabal Gattar granite occurs as disseminations and/or thin veinlets and encrustations filling some uranium mineralized fissures and fractures along the northern margin of host granite mass. In the U-poor samples, fluorite forms well-developed large crystals that are commonly zoned. The zones are represented by alternating colorless and violet zones, and the outer zones are frequently dark violet. In the U-rich samples, fluorite is usually anhedral, unzoned, and has a dark violet color. The results of analysis of REE and trace element contents of fluorites using laser ablation inductively coupled plasma mass spectrometry indicate that total REE in the anhedral unzoned fluorite are elevated compared to the well developed zoned fluorite, and also total REE in dark violet zones of zoned fluorite are elevated with respect to the colorless zones. The fluorites and host granite are generally characterized by strongly negative Eu anomalies and slightly negative or chondritic Ce anomalies. Accordingly, REE patterns of the fluorite and host granite are roughly alike, indicating that the source of REE and trace elements of hydrothermal fluids is the host granite leached by fluids. Y/Y*, Ce/Ce,* and Eu/Eu* patterns show that fluorite clearly records the compositional evolution of the hydrothermal solutions that have transferred trace and REE from host granite during the fluid–wall rocks interactions. The high uranium contents of fluorite in Gabal Gattar granite suggest that parent fluids bearing fluorine have interacted with host granite to leach uranium from the accessory minerals of granite and tetravalent uranium minerals in reduced or weakly oxidized zones.

Štěpite, U(AsO3OH)2·4H2O, from Jáchymov, Czech Republic: the first natural arsenate of tetravalent uranium

AbstractŠtěpite, tetragonal U(AsO3 OH)2(H2O)4 (IMA 2012-006), is the first natural arsenate of tetravalent uranium. It occurs in the Geschieber vein, Jáchymov ore district, Western Bohemia, Czech Republic, as emerald-green crystalline crusts on altered arsenic. Associated minerals include arsenolite, běhounekite, claudetite, gypsum, kaatialaite, the new mineral vysokýite (IMA 2012-067) and a partially characterized phase with the formula (H3O)+2(UO2)2(AsO4)2˙6H2O. Štěpite typically forms tabular crystals with prominent {001} and {010} faces, up to 0.6 mm in size. The crystals have a vitreous lustre and a grey to greenish grey streak. They are brittle with an uneven fracture and a very good cleavage on (001). Their Mohs hardness is about 2. Štěpite is not fluorescent in either short-wave or long-wave ultraviolet light. It is biaxial (–) with refractive indices (at 590 nm) of α = 1.636(2), β = 1.667(3), γ = 1.672(2) and 2Vobs < ~5°, anomalous greyish to pale yellow interference colours, and no pleochroism. The composition is as follows: 0.12Na2O, 50.19 UO2, 0.04SiO4, 0.09 P2O5, 0.93 As2O5, 1.95 SO3, 16.41 H2O; total 107.90 wt.%, yielding an empirical formula (based on 12 O a. p. f. u.) of (U1.01Na0.02)Σ1.03[(AsO3OH)1.82 (PO3OH)0.04(SO4)0.13(SiO4)0.01]Σ 2.00˙4H2O. Štěpite is tetragonal, crystallizing in space group I41/acd, with a = 10.9894(1), c = 32.9109(6) Å, V = 3974.5(1) Å3, Z = 16 and Dcalc = 3.90 g cm-3. The six strongest peaks in the X-ray powder-diffraction pattern [dobs in Å (I) (hkl)] are as follows: 8.190(100)(004), 7.008(43)(112), 5.475(18)(200), 4.111(16)(008), 3.395(20)(312,217), 2.1543(25)(419). The crystal structure of šteěpite has been solved from singlecrystal X-ray diffraction data by the charge-flipping method and refined to R1 = 0.0353 based on 1434 unique observed reflections, and to wR2 = 0.1488 for all 1523 unique reflections. The crystal structure of štšpite consists of sheets perpendicular to [001], made up of eight-coordinate uranium atoms and hydroxyarsenate 'tetrahedra'. The ligands surrounding the uranium atom consist of six oxygen atoms which belong to the hydroxyarsenate groups and two oxygen atoms which belong to interlayer H2 O molecules. Each UO8 polyhedron is connected to five other U polyhedra via six AsO3OH groups. Adjacent electroneutral sheets, of composition [U4+(AsO3OH)22-]0, are linked by hydrogen bonds involving H2 O molecules in the interlayers and OH groups in the sheets. The new mineral is named in honour of Josef Štěp (1863–1926), a Czech mining engineer and 'father' of the world's first radioactive spa at Jáchymov.

Three‐Dimensional MOF‐Type Architectures with Tetravalent Uranium Hexanuclear Motifs (U6O8)

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.