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Influence of Synthetic Conditions on Chemistry and Structural Properties of Alkaline Earth Uranyl Borates

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摘要

Four novel alkaline earth metal uranyl borates, namely, A(UO2)(5)(BO3)(2)O-2(OH)(2)center dot 5H(2)O (SrUBO-1, BaUBO-1) and A(UO2)(2)(B2O5)O (SrUBO-2, BaUBO-2) (A = Sr, Ba), have been prepared; SrUBO-1, BaUBO-1, and BaUBO-2 were synthesized using hydrothermal methods, whereas SrUBO-2 was prepared by a traditional high-temperature solid-state method. The compounds SrUBO-1 and BaUBO-1 were found to be iso-structural and crystallized in the centrosymmetric group C2/c. Their structure features two-dimensional anionic layers {(UO2)(5)(BO3)(2)O-2(OH)(2)(2-)}(n) that are composed of (UO2)(5)O-2(OH)(2)(4+) clusters and BO3(3-) polyanions. From a topological point of view, this two- dimensional anionic layer can be described as a new 4-nodal net topological type with a point symbol of {3(5).4(5)}(2){3(6).4(6).5(3)}(3){3(7).4(7).5(7)}(2). SrUBO-2 and BaUBO-2 are iso-structural and crystallized in space group C2/m. Their structures are based on a three-dimensional framework {(UO2)(2)(B2O5)O(2-)}(n). Within the three-dimensional framework, two-dimensional U(2)-U(1) = U(3) layers (L-1) with cation to cation interactions between U(3)O-2(2+) groups and one-dimensional edge sharing U(1)-U(2) chains are present. The B2O5 dimers corner sharing with U(1)-U2 chains and U(3)O-6 tetragonal bipyramids forming two-dimensional layers (L-2). L-1 further vertically interconnect with L-2 through bridging B2O5 dimers, forming a three-dimensional framework (UO2)(2)(B2O5)O(2-). The synthetic conditions, structural characterization, thermal stability, as well as spectroscopic properties of the alkaline earth metal uranyl borates are reported and discussed.

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