RESUMO
We obtained a kerosene-soluble form of the lithium salt [UO2(O2)(OH)2]24 phase (Li-U24), by adding cetyltrimethylammonium bromide surfactant to aqueous Li-U24. Interestingly, its variable-temperature solution 7Li NMR spectroscopy resolves two narrowly spaced resonances down to -10 °C, which shift upfield with increasing temperature, and finally coalesce at temperatures > 85 °C. Comparison with solid-state NMR demonstrates that the Li dynamics in the Li-U24-CTA phase involves only exchange between different local encapsulated environments. This behavior is distinct from the rapid Li exchange dynamics observed between encapsulated and external Li environments for Li-U24 in both the aqueous and the solid-state phases. Density functional theory calculations suggest that the two experimental 7Li NMR chemical shifts are due to Li cations coordinated within the square and hexagonal faces of the U24 cage, and they can undergo exchange within the confined environment, as the solution is heated. Very different than U24 in aqueous media, there is no evidence that the Li cations exit the cage, and therefore, this represents a truly confined space.
RESUMO
The fate of U(IV)O2 in the environment in a colloidal form and its dissolution and growth in controlled environments is influenced by organic ligation and redox processes, where both affect solubility, speciation, and transport. Here we investigate U(IV) aqueous speciation from pH 0 to 3 with the glycine (Gly) ligand, the smallest amino acid. We document evolution of the monomeric to the hexameric form from pH 0 to 3 via UV-vis spectroscopy and small-angle X-ray scattering (SAXS). Crystals of the hexamer [U6O4(OH)4(H2O)6(HGly)12]·12Cl-·12(H2O) (U6) were isolated at pH 2.15. The structure of U6 is a hexanuclear oxo/hydroxo cluster U6O4(OH)4 decorated by 12 glycine ligands and 6 water molecules. The effect of pH and temperature on U6 conversion to UO2 nanoparticles, or simply reversible aggregation, is detailed by transmission electron microscopy imaging, in addition to SAXS and UV-spectroscopy. Because of the zwitterion behavior of glycine, pH and temperature control over U(IV) speciation is complex. Unexpectedly, stability of the polynuclear cluster actually increases with increased pH. Speciation is sensitive to not only metal-oxo hydrolysis but also ligand lability and hydrophobic ligand-ligand interactions.
