RESUMO
Spectator ions have known and emerging roles in aqueous metal-cation chemistry, respectively directing solubility, speciation, and reactivity. Here, we isolate and structurally characterize the last two metastable members of the alkali uranyl triperoxide series, the Rb+ and Cs+ salts (Cs-U1 and Rb-U1). We document their rapid solution polymerization via small-angle X-ray scattering, which is compared to the more stable Li+, Na+ and K+ analogues. To understand the role of the alkalis, we also quantify alkali-hydroxide promoted peroxide deprotonation and decomposition, which generally exhibits increasing reactivity with increasing alkali size. Cs-U1, the most unstable of the uranyl triperoxide monomers, undergoes ambient direct air capture of CO2 in the solid-state, converting to Cs4[UVIO2(CO3)3], evidenced by single-crystal X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. We have attempted to benchmark the evolution of Cs-U1 to uranyl tricarbonate, which involves a transient, unstable hygroscopic solid that contains predominantly pentavalent uranium, quantified by X-ray photoelectron spectroscopy. Powder X-ray diffraction suggests this intermediate state contains a hydrous derivative of CsUVO3, where the parent phase has been computationally predicted, but not yet synthesized.
RESUMO
A new uranyl tetra-chloride salt with chemical formula, (NH4)2[UO2Cl4]·2H2O, namely, di-ammonium uranyl tetra-chloride dihydrate, 1, was prepared and crystallized via slow evaporation from a solution of 2 M hydro-chloric acid. As confirmed by powder X-ray diffraction, the title compound crystallizes with an ammonium chloride impurity that formed as a result of the breakdown of a triazine precursor. The (UO2Cl4)2- dianion is charge balanced by ammonium cations, while an extensive hydrogen-bond network donated from structural water mol-ecules stabilize the overall assembly. Compound 1 adds to the extensive collection of actinyl tetra-chloride salts, but it represents the first without an alkali cation for purely inorganic compounds. Diffuse reflectance and luminescence spectra show typical absorption and emission behavior, respectively, of uranyl materials.
RESUMO
Mechanochemistry enables transformations of highly insoluble materials such as uranium dioxide or the mineral studtite [(UO2)(O2)(H2O)2]·(H2O)2 into uranyl triperoxide compounds that can subsequently assemble into hydroxide-bridged uranyl peroxide dimers in the presence of lithium hydroxide. Dissolution of these solids in water yields uranyl peroxide nanoclusters including U24, Li24[(UO2)(O2)(OH)]24. Insoluble uranium solids can transform into highly soluble uranyl peroxide phases in the solid state with miniscule quantities of water. Such reactions are potentially applicable to uranium processing in the front and back end of the nuclear fuel cycle.
RESUMO
Two uranyl vanadate heteropolyoxometalates (h-POMs) have been synthesized by ionothermal methods using the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate (EMIm-Et2PO4). The hybrid actinide-transition metal shell structures have cores of (UO2)8(V6O22) and (UO2)6(V3O12), which we designate as {U8V6} and {U6V3}, respectively. The diethyl phosphate anions of the ionic liquids in some cases terminate the core structures to form actinyl oxide clusters, and in other cases the diethyl phosphate oxyanions link these cluster cores into extended structures. Three compounds exist for the {U8V6} cluster core: {U8V6}-monomer, {U8V6}-dimer, and {U8V6}-chain. Tungsten atoms can partially substitute for vanadium in the {U6V3} cluster, which results in a chain-based structure designated as {U6V3}-W. Each of these compounds contains charge-balancing EMIm cations from the ionic liquid. These compounds were characterized crystallographically, spectroscopically, and by mass spectrometry.
RESUMO
The title phospho-nate-based organic-inorganic hybrid framework, poly[bis(dimethylammonium) [(µ4-2,5-dihydroxybenzene-1,4-diphosphonato)zinc(II)]], {(C2H8N)2[Zn(C6H4O8P2)]} n , was formed unexpectedly when di-methyl-ammonium cations were formed from the in situ deca-rbonylation of the N,N-di-methyl-formamide solvent. The framework is built up from ZnO4 tetra-hedra and bridging di-phospho-nate tetra-anions to generate a three-dimensional network comprising [100] channels occupied by the (CH3)2NH2 + cations. Within the channels, an array of N-Hâ¯O hydrogen bonds help to establish the structure. In addition, intra-molecular O-Hâ¯O hydrogen bonds between the appended -OH groups of the phenyl ring and adjacent PO3 2- groups are observed.