Functionalization of Borate Networks by the Incorporation of Fluoride: Syntheses, Crystal Structures, and Nonlinear Optical Properties of Novel Actinide Fluoroborates

Wang, S. A., Alekseev, E. V., Juan, D. W., Miller, H. M., Oliver, A. G., Liu, G. K., Depmeier, W. and Albrecht-Schmitt, T. E. (2011) Functionalization of Borate Networks by the Incorporation of Fluoride: Syntheses, Crystal Structures, and Nonlinear Optical Properties of Novel Actinide Fluoroborates Chemistry of Materials, 23 (11). pp. 2931-2939. DOI 10.1021/cm2004984.

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Abstract

The boric acid flux reactions of uranyl nitrate with sodium, potassium, rubidium, or thallium fluoride result in the formation of a novel family of uranyl(VI) fluoroborate materials. These compounds are Na[(UO(2))B(5)O(8)(OH)F]center dot H(2)O (NaUBOF-1), K[(UO(2))B(5)O(8)(OH)F] (KUBOF-1), K(11)[(UO(2))(6)B(24)O(36)F(22))](H(2)BO(3)) (KUBOF-2), Rb[(UO(2))B(5)O(8)(OH)F] (RbUBOF-1), and Tl[(UO(2))B(5)O(8)(OH)F] (TlUBOF-1). A new neptunium(VI) fluoroborate that is isotypic with NaUBOF-1, Na[(NpO(2))B(5)O(8)(OH)F]center dot H(2)O (NaNpBOF-1), was synthesized via the boric acid flux reaction of neptunium(VI) nitrate with sodium fluoride. These new actinide fluoroborates share a common structural motif consisting of a linear actinyl (U(Np)O(2)(2+)) cation surrounded by BO(3) triangles and BO(4) tetrahedra to create an U(Np)O(8) hexagonal bipyramidal environment around uranium or neptunium. The borate anions bridge between actinyl units to create layers. B-F bonds were formed during the reactions to yield BO(3)F tetrahedral units. The BO(3)F tetrahedra and additional BO(3) triangles extend from the actinyl polyborate layers and are directed approximately perpendicular to the layers. A novel actinyl borate layered topology was found in K(11)[(UO(2))(6)B(24)O(36)F(22))](H(2)BO(3)) (KUBOF-2). Except for K[(UO(2))B(5)O(8)(OH)F] (KUBOF-1) and K(11)[(UO(2))(6)(-) B(24)O(36)F(22))](H(2)BO(3)) (KUBOF-2), all of the other actinide fluoroborate phases adopt noncentrosymmetric space groups. TL[(UO(2))B(5)O(8)(OH)F] (TlUBOF-1), which can be obtained as a pure phase, displays second-harmonic generation of 532-nm light from 1064-nm light.

Document Type: Article
Keywords: actinide borate uranium borate neptunium borate fluoroborate noncentrosymmetric materials nonlinear optical materials sharing bo4 tetrahedra neptunium spectroscopy parameters chemistry oxoborate pressure topology insights uranium
Research affiliation: Kiel University
DOI etc.: 10.1021/cm2004984
ISSN: 0897-4756
Date Deposited: 15 Dec 2011 05:15
Last Modified: 08 Oct 2012 09:27
URI: http://eprints.uni-kiel.de/id/eprint/15662

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