Uranyl Compounds Research Articles

Cinnamic Acid: A Low-Toxicity Natural Bidentate Ligand for Uranium Decorporation.

Uranium accumulation in the kidneys and bones following internal contamination results in severe damage, emphasizing the pressing need for the discovery of actinide decorporation agents with efficient removal of uranium and low toxicity. In this work, cinnamic acid (3-phenyl-2-propenoic acid, CD), a natural aromatic carboxylic acid, is investigated as a potential uranium decorporation ligand. CD demonstrates markedly lower cytotoxicity than that of diethylenetriaminepentaacetic acid (DTPA), an actinide decorporation agent approved by the FDA, and effectively removes approximately 44.5% of uranyl from NRK-52E cells. More importantly, the results of the prompt administration of the CD solution remove 48.2 and 27.3% of uranyl from the kidneys and femurs of mice, respectively. Assessments of serum renal function reveal the potential of CD to ameliorate uranyl-induced renal injury. Furthermore, the single crystal of CD and uranyl compound (C9H7O2)2·UO2 (denoted as UO2-CD) reveals the formation of uranyl dimers as secondary building units. Thermodynamic analysis of the solution shows that CD coordinates with uranyl to form a 2:1 molar ratio complex at a physiological pH of 7.4. Density functional theory (DFT) calculations further show that CD exhibits a significant 7-fold heightened affinity for uranyl binding in comparison to DTPA.

Understanding solvent polarity effects on the separation of uranyl porphyrin-derivative complexes.

Solvation is a crucial task in developing efficient and selective extractants for actinide elements, but an understanding and perspective of solvent effects on the extraction of uranyl are still lacking. Herein, we present investigations into solvent effects on the geometry, stability and bonding properties of five uranyl porphyrin derivative complexes (UO2(L)) in four solvents via relativistic quantum chemical calculations, and reveal some trends in the influence of solvent polarity on uranyl compounds. All five [L]2- ligands equatorially coordinate [UO2]2+ in a hexa-dentate (κ6) fashion. Thus, the uranium center is bound to six N atoms by U-N bonds, and the properties of the U-N bond are affected by the ligands rather than by the solvent. The relative stability of these UO2(L) complexes is obviously affected by the solvent polarity; lower polar solvents stabilize more UO2(L) complexes from higher polar solvents, resulting in more extensive interaction of U-N. By computing the reaction energy, we track the conversion of pure [UO2]2+ to UO2(L) complexes in different solvents; the uranyl dipentafluorobenziamethyrin species exhibit the greatest selectivity to higher polarity solvents, with significant orbital interactions of U-N accounting for this stability and selectivity. This study provides a general procedure for theoretical screening of the binding ability and solvent selectivity of macrocyclic ligands towards uranyl, and searching for suitable ligands and solvents that will later be applied in nuclear science disciplines.

Utilizing Ionic Liquids as Bifunctional Reagents for the Ionothermal Synthesis of Uranyl Compounds

Utilizing Ionic Liquids as Bifunctional Reagents for the Ionothermal Synthesis of Uranyl Compounds

Исследование спектроскопических свойств фотонных кристаллов и наноструктур

The paper proposes substantiation of dependence of dielectric permittivity, polariton dispersion and light group velocity in the sodium uranyl acetate on the wavelength. Many bands were found in the uranyl compounds transmission and absorption spectra. It was indicated that the polariton waves group velocity was decreasing anomalously in vicinity of the resonant absorption frequencies, i.e., the light was effectively stopped. This led to abnormal increase in the efficiency between the light interaction processes and the matter. Optical properties of the one-dimensional photonic crystal film formed by electrochemical etching of aluminum foil were studied. Experimental data on the transmission and reflection spectra in the region of first, second and third stop bands of the anode photonic aluminum oxide crystal were compared with theoretical dependence obtained from the known dispersion relation. Refractive indices of the first and second layers of various thin photonic crystal films, structure period and effective refractive index of the structures were theoretically calculated. Possibility of controlling position of the stop bands of one-dimensional photonic crystals in accordance with the Wulff --- Bragg’s relation was established. The studied photonic crystals could be used in experimental setups to register the light combined scattering spectra of dielectric media in the low-frequencies region

Unveiling Structural Diversity of Uranyl Compounds of Aprotic 4,4'-Bipyridine N,N'-Dioxide Bearing O-Donors.

As an aprotic O-donor ligand, 4,4'-bipyridine N,N'-dioxide (DPO) shows good potential for the preparation of uranyl coordination compounds. In this work, by regulating reactant compositions and synthesis conditions, diverse coordination assembly between uranyl and DPO under different reaction conditions was achieved in the presence of other coexisting O-donors. A total of ten uranyl-DPO compounds, U-DPO-1 to U-DPO-10, have been synthesized by evaporation or hydro/solvothermal treatment, and the possible competition and cooperation of DPO with other O-donors for the formation of these uranyl-DPO compounds are discussed. Starting with an aqueous solution of uranyl nitrate, it is found that an anionic nitrate or hydroxyl group is involved in the coordination sphere of uranyl in U-DPO-1 ((UO2)(NO3)2(H2O)2·(DPO)), U-DPO-2 ((UO2)(NO3)2(DPO)), and U-DPO-3 ((UO2)(DPO)(μ2-OH)2), where DPO takes three different kinds of coordination modes, i.e. uncoordinated, monodentate, and biconnected. The utilization of UO2(CF3SO3)2 in acetonitrile, instead of an aqueous solution of uranyl nitrate, precludes the participation of nitrate and hydroxyl, and ensures the engagement of DPO ligands (4-5 DPO ligands for each uranyl) in a uranyl coordination sphere of U-DPO-4 ([(UO2)(CF3SO3)(DPO)2](CF3SO3)), U-DPO-5 ([UO2(H2O)(DPO)2](CF3SO3)2) and U-DPO-6 ([(UO2)(DPO)2.5](CF3SO3)2). Moreover, when combined with anionic carboxylate ligands, terephthalic acid (H2TPA), isophthalic acid (H2IPA), and succinic acid (H2SA), DPO works well with them to produce four mixed-ligand uranyl compounds with similar structures of two-dimensional (2D) networks or three-dimensional (3D) frameworks, U-DPO-7 ((UO2)(TPA)(DPO)), U-DPO-8 ((UO2)2(DPO)(IPA)2·0.5H2O), U-DPO-9 ((UO2)(SA)(DPO)·H2O), and U-DPO-10 ((UO2)2(μ2-OH)(SA)1.5(DPO)). Density functional theory (DFT) calculations conducted to probe the bonding features between uranyl ions and different O-donor ligands show that the bonding ability of DPO is better than that of anionic CF3SO3 -, nitrate, and a neutral H2O molecule and comparable to that of an anionic carboxylate group. Characterization of physicochemical properties of U-DPO-7 and U-DPO-10 with high phase purity including infrared (IR) spectroscopy, thermogravimetric analysis (TGA), and luminescence properties is also provided.

Modulating the coordination microenvironment of uranyl compounds to enhance photocatalytic CO2 reduction

Variation of the coordination microenvironment of actinide metal uranyl affects the photocatalytic CO2 reduction performance of materials.

U(VI) Coordination Modes in Complex Uranium Silicates: Cs[(UO6)2(UO2)9(Si2O7)F] and Rb2[(PtO4)(UO2)5(Si2O7)

Crystals of two new inorganic uranyl silicates, Cs[(UO6)2(UO2)9(Si2O7)F] (1) and Rb2[(PtO4)(UO2)5(Si2O7)] (2), were produced from melts in evacuated silica tubes. Their structures have been solved by direct methods: 1 is trigonal, P-31c, a = 10.2040(3), c = 17.1278(5) Å, V = 1544.45(10) Å3, R1 = 0.042; 2 is tetragonal, P4/mbm, a = 16.0400(24), c = 3.9231(6) Å, V = 1009.34(10) Å3, R1 = 0.045. 1 is the first example of cation–cation interactions between the uranyl polyhedra in uranyl silicates. Therein, UVI adopts three coordination modes, UO6 octahedra, UO6F, and UO7 pentagonal bipyramids, with the latter sharing common edges to form U2O12 dimers. Three dimers associate into six-membered rings via cation–cation interactions. The structure of 1 can be described as a complex uranyl fluoride silicate framework with channels filled by the U1 atoms and disordered Cs+ cations. 2 represents a new type of topology never observed before among the structures of uranyl compounds; it is also a first complex uranium platinum oxide. Therein, the UO6 tetragonal bipyramids share edges to form chains. Five such chains are stitched into a complex ribbon via the silicon polyhedra. The ribbons are connected into a framework by the PtO4 squares; rubidium atoms are located in the channels of the framework.

Investigations of the Cobalt Hexamine Uranyl Carbonate System: Understanding the Influence of Charge and Hydrogen Bonding on the Modification of Vibrational Modes in Uranyl Compounds.

Hydrogen bonding networks within hexavalent uranium materials are complex and may influence the overall physical and chemical properties of the system. This is particularly true if hydrogen bonding takes places between the donor and the oxo group associated with the uranyl cation (UO22+). In the current study, we evaluate the impact of charge-assisted hydrogen bonding on the vibrational modes of the uranyl cation using uranyl tricarbonate [UO2(CO3)3]4– interactions with [Co(NH3)6]3+ as the model system. Herein, we report the synthesis and structural characterization of five novel compounds, [Co(NH3)6]Cl(CO3) (Co_Cl_CO3), [Co(NH3)6]4[UO2(CO3)3]3(H2O)11.67 (Co4U3), [Co(NH3)6]3[UO2(CO3)3]2Cl (H2O)7.5 (Co3U2_Cl), [Co(NH3)6]2[UO2(CO3)3]Cl2 (Co2U_Cl), and [Co(NH3)6]2[UO2(CO3)3]CO3 (Co2U_CO3), which contain differences in the crystalline packing and extended hydrogen bonding networks. We show that these slight changes in the supramolecular assembly and hydrogen bonding networks result in the modification of modes as observed by infrared and Raman spectroscopy. We use density functional theory calculations to assign the vibrational modes and provide an understanding about how uranyl bond perturbation and changes in hydrogen bonding interactions can impact the resulting spectroscopic signals.

Exploring the Role of Organic Functional Groups in the Ionothermal Synthesis of Uranyl Phosphate Materials

AbstractFour new hybrid organic‐inorganic uranyl phosphate compounds were structurally characterized after single crystals were grown via ionothermal synthesis using the ionic liquids 1‐ethyl‐3‐methylimidazolium dimethyl phosphate and 1‐ethyl‐3‐methylimidazolium dibutyl phosphate. Three of the new crystal structures presented here incorporate dimethyl or monomethyl phosphate ligands into the structural unit to form one chain‐based compound and two sheet‐based compounds. One of the structures utilizes dibutyl phosphate to form a previously reported uranyl compound, a structural polymorph that crystallized in space groupP21/cin contrast to the previously reportedP‐1 structure. The structural and topological relationships are compared to those of uranyl phosphate minerals as well as previously reported organophosphate compounds. The roles of the organics on the phosphate anions in impacting uranyl coordination and stabilizing the crystal structures are discussed.

Research progress of SERS on uranyl ions and uranyl compounds: a review

The direct detection method possesses the ability of both content detection of uranyl ions and structural analysis of uranyl compounds in nmol level, while the indirect detection method can detect the uranyl ions as low as fmol level.

Impact of the proximity effect on uranyl coordination of conformationally variable weakly-bonded cucurbit[6]uril-bipyridinium pseudorotaxane

In this work, it has been demonstrated that weakly-bonded CB[6]-bipyridinium pseudorotaxanes exhibit various coordination mode in the assembly with uranyl, resulting in abundant structure variety in the prepared uranyl compounds.

Mixed-Ligand Uranyl Squarate Coordination Polymers: Structure Regulation and Redox Activity.

The electron-rich squarate ion (C4O42-, SA2-) possesses electronic delocalization over the entire molecule and good redox activity, and the functionalization of metal-organic complexes with the SA2- group is desirable. In this work, a mixed-ligand method is used to construct novel uranyl squarate coordination polymers utilizing 4,4'-bipyridine (bpy), 4,4'-bipyridine-N,N'-dioxide (bpydo), 1,10-phenanthroline (phen), 4,4'-vinylenedipyridine (vidpy), and in situ formed oxalate (OA2-) as ancillary ligands. Seven mixed-ligand uranyl compounds, [(UO2)(OH)(SA)](Hbpy) (1), [(UO2)(H2O)(SA)2](H2bpy) (2), (UO2)(H2O)(SA)(bpydo)·2H2O (3), (UO2)(H2O)(SA)(phen)·H2O (4), (UO2)(OH)(SA)0.5(phen)·H2O (5), [(UO2)(SA)(OA)0.5](Hphen) (6), and [(UO2)(SA)(OA)0.5](Hvidpy) (7), with varying crystal structures were synthesized under hydrothermal conditions. Compound 1, together with bpy molecules filling in the interlayer space as template agents, has a two-dimensional (2D) network structure, while 2 gives a one-dimensional (1D) chain based on mononuclear uranium units. Compound 3 shows a neutral 2D network through the combined linkage of SA2- and bpydo. Both 4 and 5 have a similar chain-like structure due to the capping effect of phen motifs, while phen molecules in 6 act as templating agents after protonation. Similar to 6, compound 7 has a "sandwich-like" structure in which the Hvidpy motifs locate in the voids of layers of 2D uranyl-squarate networks. The redox properties of typical mixed-ligand uranyl-squarate compounds, 1, 4, and 5 with high phase purity, are characterized using cyclic voltammetry. All three of these uranyl coordination compounds show anode peaks (Ea) at 0.777, 0.804, and 0.760 V, respectively, which correspond to the oxidation process of SA2- → SA. Meanwhile, cathodic peaks (Ec) at -0.328, -0.315, and -0.323 V corresponding to the reduction process of U(VI) → U(V) are also observed. The results reveal that all three of these uranyl coordination compounds show good redox activity and, most importantly, the interplay between two different redox-active motifs of SA2- organic linker and uranyl node. This work enriches the library of redox-active uranyl compounds and provides a feasible mixed-ligand method for regulating the synthesis of functional actinide compounds.

Secondary Role of Aliphatic and Heterocyclic Amines in the Formation of Low-Temperature Amine-Bearing U, Np, and Pu(VI) Chromates.

Uranyl compounds with tetrahedral oxoanions demonstrate a significant structural and topological diversity. Complexes of transuranium elements with such anions are not equally well-represented in the literature. To answer the question about the structural similarity in a series of An6+ complexes with XO42- anions, we synthesized and studied 10 new U, Np, and Pu chromates with outer-sphere organic cations. The structural analysis and comparison with the literature data shows that the Np and Pu complexes are generally based on the same structural blocks as the uranyl compounds. Moreover, the chromate anion does not show any unique structural role as compared to the sulfate and selenate ions. As a result, the neptunium and plutonium chromates contain 1D and 2D structural units similar to those found in the uranyl sulfates and selenates. The templating role of the outer-sphere cations in the actinyl complexes with tetrahedral oxoanions is also not evident, and there is no clear correlation between the nature of the outer-sphere cations and the topology of the structural units.

Uranyl(VI) Triflate as Catalyst for the Meerwein-Ponndorf-Verley Reaction.

Catalytic transformation of oxygenated compounds is challenging in f-element chemistry due to the high oxophilicity of the f-block metals. We report here the first Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl substrates with uranium-based catalysts, in particular from a series of uranyl(VI) compounds where [UO2(OTf)2] (1) displays the greatest efficiency (OTf = trifluoromethanesulfonate). [UO2(OTf)2] reduces a series of aromatic and aliphatic aldehydes and ketones into their corresponding alcohols with moderate to excellent yields, using iPrOH as a solvent and a reductant. The reaction proceeds under mild conditions (80 °C) with an optimized catalytic charge of 2.3 mol % and KOiPr as a cocatalyst. The reduction of aldehydes (1-10 h) is faster than that of ketones (>15 h). NMR investigations clearly evidence the formation of hemiacetal intermediates with aldehydes, while they are not formed with ketones.

Proximity Effect in Uranyl Coordination of the Cucurbit[6]uril-Bipyridinium Pseudorotaxane Ligand for Promoting Host-Guest Synergistic Chelating.

In the present work, we proposed regulating uranyl coordination behavior of cucurbituril-bipyridinium pseudorotaxane ligand by utilizing meta-functionalized bipyridinium dicarboxylate guest. A tailored pseudorotaxane precursor involving 1,1'-(hexane-1,6-diyl)bis(3-cyanopyridin-1-ium) bromide (C6BPCN3) and cucurbit[6]uril (CB[6]) has designed and synthesized. Through in situ hydrolysis of the pseudorotaxane ligands and their coordination assembly with uranyl cations, seven new uranyl-rotaxane coordination polymers URCP1-URCP7 have been obtained under hydrothermal conditions in the presence of different anions. It is demonstrated that the variation of carboxylate groups from para- to meta-position greatly affected the coordination behaviors of the meta-functionalized pseudorotaxane linkers, which are enriched from simple guest-only binding to host-guest simultaneous coordination and synergistic chelating. This effective regulation on uranyl coordination of supramolecular pseudorotaxane can be attributed to the proximity effect, which refers to the meta-position carboxyl group being spatially closer to the portal carbonyl group of CB[6]. Moreover, by combining other regulation methods such as introducing competing counterions and modulating solution acidity, the nuclearity of the uranyl center and the coordination patterns of the pseudorotaxane ligand can be diversely tuned, which subsequently exert great influence on the final dimensionality of resultant uranyl compounds. This work presents a large diversity of uranyl-based coordination polyrotaxane compounds with fascinating mechanically interlocked components and, most importantly, provides a feasible approach to adjust and control the metal coordination behavior of the pseudorotaxane ligand that might expand the scope of application of such supramolecular ligands.

Mild hydrothermal synthesis of potassium uranyl phosphates with layered and framework structures

Two new potassium uranyl phosphates, K2(UO2)2(HPO4)3·2H2O and K4(UO2)6(H2O)2(PO4)2(HPO4)5·3H2O were synthesized under mild hydrothermal conditions. K2(UO2)2(HPO4)3·2H2O crystallizes in the orthorhombic space group Pbca with lattice parameters a ​= ​20.5125(5) Å, b ​= ​15.0951(4) Å, and c ​= ​11.0103(3) Å and K4(UO2)6(H2O)2(PO4)2(HPO4)5·3H2O crystallizes in the orthorhombic space group Pbcm with lattice parameters a ​= ​10.9228(4) Å, b ​= ​26.8147(10) Å, and c ​= ​13.5379(5) Å. Both form in new structure types with the prior having a layered structure and the latter a framework structure. Both compounds exhibit intense fluorescence typical of uranyl compounds. Thermal analysis of each compound indicated two weight loss events up to 700 ​°C, one associated with dehydration of the structure and one that is likely the result of condensation of the HPO4 units. Exfoliation of the layers in K2(UO2)2(HPO4)3·2H2O is achieved using TMAH as an exfoliating agent.

Temperature-Triggered Structural Dynamics of Non-Coordinating Guest Moieties in a Fluorescent Actinide Polyrotaxane Framework.

We present here the synthesis of a novel fluorescent actinide polyrotaxane compound URCP1 through the utilization of an end-cutting pseudorotaxane precursor with only the cucurbit[6]uril (CB[6]) macrocyclic components acting as linking struts. The non-coordinating guest motif in the obtained polyrotaxane, with increased freedom and structural flexibility, can display intriguing temperature-triggered conformational variations inside the cavity of CB[6], which was clearly evidenced by crystallographic snapshots at different temperatures. Notably, this observation of temperature-triggered structural dynamics in URCP1 represents the first report of actinide polyrotaxane with such feature in solid-state. Moreover, URCP1 has a high photoluminescence quantum yield (PLQY) of 49.8 %, comparable to other luminescent uranyl compounds, and can work as a fluorescent probe to selectively detect Fe3+ over other eight competing cations in aqueous solution, with the limit of detection being as low as 4.4×10-3 ppm.

Construction of Hybrid Bimetallic Uranyl Compounds Based on a Preassembled Terpyridine Metalloligand.

Six hybrid uranyl-transition metal compounds [UO2 Ni(cptpy)2 (HCOO)2 (DMF)(H2 O)] (1), [UO2 Ni(cptpy)2 (BTPA)2 ] (2), [UO2 Fe(cptpy)2 (HCOO)2 (DMF)(H2 O)] (3), [UO2 Fe(cptpy)2 (BTPA)2 ] (4), [UO2 Co(cptpy)2 (HCOO)2 (DMF)(H2 O)] (5), and [UO2 Co(cptpy)2 (BTPA)2 ] (6), based on bifunctional ligand 4'-(4-carboxyphenyl)-2,2':6',2''-terpyridine (Hcptpy) are reported (H2 BTPA = 4,4'-biphenyldicarboxylic acid). Single-crystal XRD revealed that all six compounds feature similar metalloligands, which consist of two cptpy- anions and one transition metal cation. The metalloligand M(cptpy)2 can be considered to be an extended linear dicarboxylic ligand with length of 22.12 Å. Compounds 1, 3, and 5 are isomers, and all of them feature 1D chain structures. The adjacent 1D chains are connected together by hydrogen bonds and π-π interactions to form a 3D porous structure, which is filled with solvent molecules and can be exchanged with I2 . Compounds 2, 4, and 6 are also isomers, and all of them feature 2D honeycomb (6,3) networks with hexagonal units of dimensions 41.91×26.89 Å, which are the largest among uranyl compounds with honeycomb networks. The large aperture allows two sets of equivalent networks to be entangled together to result in a 2D+2D→3D polycatenated framework. Remarkably, these uranyl compounds exhibit high catalytic activity for cycloaddition of carbon dioxide. Moreover, the geometric and electronic structures of compounds 1 and 2 are systematically discussed on the basis of DFT calculations.

Matrix-Assisted Ionization of Molecular Uranium Species.

Matrix-assisted ionization (MAI) demonstrates high sensitivity for a variety of organic compounds; however, few studies have reported the application of MAI for the detection and characterization of inorganic analytes. Trace-level uranium analysis is important in the realms of nuclear forensics, nuclear safeguards, and environmental monitoring. Traditional mass spectrometry methods employed in these fields require combinations of extensive laboratory chemistry sample preparation and destructive ionization methods. There has been recent interest in exploring ambient mass spectrometry methods that enable timely sample analysis and higher sensitivity than what is attainable by field-portable radiation detectors. Rapid characterization of uranium at nanogram levels is demonstrated in this study using MAI techniques. Mass spectra were collected on an atmospheric pressure mass spectrometer for solutions of uranyl nitrate, uranyl chloride, uranyl acetate, and uranyl oxalate utilizing 3-nibrobenzonitrile as the ionization matrix. The uranyl complexes investigated were detectable, and the chemical speciation was preserved. Sample analysis was accomplished in a matter of seconds, and limits of detection of 5 ng of uranyl nitrate, 10 ng of uranyl oxalate, 100 ng of uranyl chloride, and 200 ng of uranyl acetate were achieved. The observed gas-phase speciation was similar to negative-ion electrospray ionization of uranyl compounds with notable differences. Six matrix-derived ions were detected in all negative-ion mass spectra, and some of these ions formed adducts with the uranyl analyte. Subsequent analysis of the matrix suggests that these molecules are not matrix contaminants and are instead created during the ionization process.

Unprecedented Catalytic Behavior of Uranyl(VI) Compounds in Chemical Reactions

Uranyl catalysis represents a progressively more significant class of current research. The key species responsible for such catalysis is UO22+ ion which is a remarkably stable molecular component possessing strongly covalent and chemically robust trans U‐oxo groups. Aside from its fundamental interest, an understanding of the chemistry of such divalent UO22+ ion is enviable due to its huge ecological importance. The unprecedented electronic non‐rigidity of uranium center with easy switching among oxidation states and kinetic lability of its coordination states are the key features to bring about a considerable development in its catalytic reactivity profiles. This review explores the topical evolutions of most promising uranyl(VI) catalytic systems appearing in the literature for the last two decades along with reports prior to 2000 incorporated where pertinent. In addition to homometallic uranyl catalysis, a succinct discussion on heterometallic uranyl catalysis is presented. Finally, some relevant comparisons have been made between the uranyl catalysis and transition metal systems.