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Three-Dimensional Network of Cation–Cation-Bound Neptunyl(V) Squares: Synthesis and in Situ Raman Spectroscopy Studies

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posted on 17.02.2016, 00:00 by Geng Bang Jin
Cation–cation interactions (CCIs) are an essential feature of actinyl chemistry, particularly neptunyl­(V). To better understand the formation mechanisms of CCIs, the crystallization process of Np­(V) CCI compounds has been explored during the evaporation of acidic Np­(V) stock solutions using X-ray diffraction and both ex situ and in situ Raman spectroscopy. At least four Np solid products have been isolated from evaporation of the same Np­(V) acidic solution. In situ evaporation using a continuous wave laser (532 nm) as a local heat source produced similar solid products to ex situ experiments with matching Raman signatures. The formation of these products is highly dependent on the evaporation conditions. Slower evaporation appears to favor the formation of a new neptunyl­(V) compound, (NpO2)­Cl­(H2O)2 (1), over other solid products. The structure of 1 features a three-dimensional network of NpO2+ cations, where neighboring Np­(V) ions are only connected to each other through CCIs in a square arrangement. The ONpO stretching region shows similar Raman bands in both the solids and solution suggesting that CCIs between Np­(V) cations exist prior to crystallization. These results provide new insight into the formation mechanism of Np­(V) CCI compounds from solutions.