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DOE OSTI2014

The influence of pressure on the structure of a 2D uranium(VI) carboxyphosphonoate compound

We report the first quantitative analysis of the structural evolution of a uranyl bearing coordination polymer in response to pressure. The material that is central to this study, (UO{sub 2})(O{sub 3}PCH{sub 2}CO{sub 2}H) (1), is constructed from rigid 2D inorganic layers comprising edge sharing UO{sub 7} pentagonal bipyramids cross-linked by [PO{sub 3}(COOH)]{sup 2−} anions. Strong hydrogen bonding interactions exist between the pendent carboxylic acid groups on adjacent layers. Under pressure, 1 exhibits compressional behaviour primarily in the direction perpendicular to the inorganic layers, which is aided by a reduction in the interlayer distance and shifting of the layers with respect to each other. The bulk modulus for the 2D compound 1 is unexpectedly high [18.1(1) GPa] and is within the range reported for 3D CPs assembled from Zn{sup II} cations and inflexible imidazolate anions, and is at the lower end of the range of moduli observed for aluminosilicate zeolites (19–59 GPa). - Graphical Abstract: The compression mechanism and elastic constants for a 2D Uranium(VI) carboxyphosphonoate compound are reported. - Highlights: • The response to pressure of a uranium carboxyphosphonoate compound has been studied. • High-pressure single-crystal XRD data for this 2D uranium compound were collected. • Elastic constants for this material have been determined. • The compression mechanism for the compound has been elucidated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗