Structure-Property Relationships in Lithium, Silver, and Cesium Uranyl Borates

Wang, S. A., Alekseev, E. V., Stritzinger, J. T., Liu, G. K., Depmeier, W. and Albrecht-Schmitt, T. E. (2010) Structure-Property Relationships in Lithium, Silver, and Cesium Uranyl Borates Chemistry of Materials, 22 (21). pp. 5983-5991. DOI 10.1021/cm1022135.

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Abstract

Four new uranyl borates, Li[UO(2)B(5)O(9)]center dot H(2)O (LiUBO-1), Ag[(UO(2))B(5)O(8)(OH)(2)] (AgUBO-1), alpha-Cs[(UO(2))(2))B(11)O(16)(OH)(6)] (CsUBO-1), and beta-Cs[(UO(2))(2)B(11)O(16)(OH)(6)] (CsUBO-2) were synthesized via the reaction of uranyl nitrate with a large excess of molten boric acid in the presence of lithium, silver, or cesium nitrate. These compounds share a common structural motif consisting of a linear uranyl, UO(2)(2+), cation surrounded by BO(3) triangles and BO(4) tetrahedra to create an UO(8) hexagonal bipyramidal environment around uranium. The borate anions bridge between uranyl units to create sheets. Additional BO(3) triangles extend from the polyborate layers, and are directed approximately perpendicular to the sheets. In Li[(UO(2))B(5)O(9)]center dot H(2)O, the additional BO(3) triangles connect these sheets together to form a three-dimensional framework structure. Li[(UO(2))B(5)O(9)]center dot H(2)O and beta-Cs[(UO(2))(2)B(11)O(16)(OH)(6)] adopt noncentrosymmetric structures, while Ag[(UO(2))B(5)O(8)(OH)(2)] and alpha-Cs[(UO(2))(2))B(11)O(16)(OH)(6)]are centrosymmetric. Li[(UO(2))B(5)O(9)]center dot H(2)O, which can be obtained as pure phase, displays second-harmonic generation of 532 nm light from 1064 mu light. Topological relationships of all actinyl borates are developed.

Document Type: Article
Keywords: fundamental building-blocks nonlinear-optical materials transition-metal-complexes open-framework vanadium borophosphate crystal-chemistry nuclear-waste boric-acid borogermanate channels
Research affiliation: Kiel University
Refereed: Yes
DOI etc.: 10.1021/cm1022135
ISSN: 0897-4756
Date Deposited: 22 Dec 2011 06:01
Last Modified: 28 Mar 2018 10:22
URI: http://eprints.uni-kiel.de/id/eprint/15729

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