Incorporation of Mn(II) and Fe(II) into Uranyl Carboxyphosphonates

Alsobrook, A. N., Alekseev, E. V., Depmeier, W. and Albrecht-Schmittt, T. E. (2011) Incorporation of Mn(II) and Fe(II) into Uranyl Carboxyphosphonates Crystal Growth & Design, 11 (6). pp. 2358-2367. DOI 10.1021/cg200127a.

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Abstract

Five heterobimetallic U(VI)/M(II) (M = Mn, Fe) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO(3), triethyl phosphonoacetate, with either Mn(II) or Fe(II) acetate. The manganese reactions yield Mn(2)[(UO(2))(6)(PO(3)CH(2)-CO(2))(3)O(3)(OH)(H(2)O)(2)]center dot 16H(2)O (MnUPAA-1) and [Mn(H(2)O)(6)][Mn(H(2)O)(5)Mn(2)(UO(2))(5)(PO(3)CH(2)CO(2))(6)(H(2)O)]ce nter dot 5.75H(2)O (MnUPAA-2). The addition of boric acid, which lowers the crystallization temperature, allows for the production of a third product, [Mn(H(2)O)(4)](2)(UO(2))(3)(PO(3)CH(2)CO(2))(2)O(2) (MnUPAA-3). The iron-containing reactions yield [Fe(H(2)O)(6)][UO(2)(PO(3)CH(2)CO(2))](2)center dot 8H(2)O (FeUPAA-1) and [Fe(H(2)O)(6)][UO(2),(PO(3)CH(2)CO(2))H(2)O](2)center dot 4H(2)O (FeUPAA-2). Four of these five compounds crystallize in low-symmetry space groups; whereas MnUPAA-1 crystallizes in the cubic space group Im (3) over bar and possesses a remarkably complex open-framework structure containing both UO(7) pentagonal bipyramids and UO(8) hexagonal bipyramids. MnUPAA-3 adopts a one-dimensional uranium oxide topology that contains both UO(6) tetragonal bipyramids and UO(7) pentagonal bipyramids. The remaining three compounds solely contain UO(7) pentagonal bipyramids.

Document Type: Article
Keywords: templated uranium sulfates bond-valence parameters crystal-chemistry hydrothermal synthesis structural variation magnetic-properties composition space molybdates phosphates fluorides
Research affiliation: Kiel University
DOI etc.: 10.1021/cg200127a
ISSN: 1528-7483
Date Deposited: 15 Dec 2011 05:28
Last Modified: 08 Oct 2012 09:26
URI: http://eprints.uni-kiel.de/id/eprint/15607

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