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Title: Uranyl carboxyphosphonates that incorporate Cd(II)

Abstract

The hydrothermal treatment of UO{sub 3}, Cd(CH{sub 3}CO{sub 2}){sub 2}.2H{sub 2}O, and triethyl phosphonoacetate results in the formation of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O (CdUPAA-1), [Cd{sub 3}(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 6}(H{sub 2}O){sub 13}].6H{sub 2}O (CdUPAA-2), and Cd(H{sub 2}O){sub 2}[(UO{sub 2})(PO{sub 3}CH{sub 2}CO{sub 2})(H{sub 2}O)]{sub 2} (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO{sub 7} pentagonal bipyramids and UO{sub 8} hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 A across that are filled with disordered water molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO{sub 7} pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together. -- Graphical abstract: A view of part of the cubic structure of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O. Display Omitted highlights: > High symmetry uranyl compounds. > Three-dimensional structures. > Porous materials. >more » Heterobimetallic compounds.« less

Authors:
 [1]; ;  [2];  [1];  [3]
  1. Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556 (United States)
  2. Institut fuer Geowissenschaften, Universitaet zu Kiel, 24118 Kiel (Germany)
  3. (United States)
Publication Date:
OSTI Identifier:
21504073
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 184; Journal Issue: 5; Other Information: DOI: 10.1016/j.jssc.2011.03.026; PII: S0022-4596(11)00123-X; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CADMIUM COMPLEXES; CATIONS; LAYERS; ORGANOMETALLIC COMPOUNDS; PHOSPHONATES; POROUS MATERIALS; TRIGONAL LATTICES; URANIUM TRIOXIDE; URANYL COMPOUNDS; ACTINIDE COMPOUNDS; CHALCOGENIDES; CHARGED PARTICLES; COMPLEXES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; IONS; MATERIALS; ORGANIC COMPOUNDS; ORGANIC PHOSPHORUS COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; URANIUM COMPOUNDS; URANIUM OXIDES

Citation Formats

Alsobrook, Andrea N., Alekseev, Evgeny V., Depmeier, Wulf, Albrecht-Schmitt, Thomas E., E-mail: talbrec1@nd.ed, and Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556. Uranyl carboxyphosphonates that incorporate Cd(II). United States: N. p., 2011. Web. doi:10.1016/j.jssc.2011.03.026.
Alsobrook, Andrea N., Alekseev, Evgeny V., Depmeier, Wulf, Albrecht-Schmitt, Thomas E., E-mail: talbrec1@nd.ed, & Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556. Uranyl carboxyphosphonates that incorporate Cd(II). United States. doi:10.1016/j.jssc.2011.03.026.
Alsobrook, Andrea N., Alekseev, Evgeny V., Depmeier, Wulf, Albrecht-Schmitt, Thomas E., E-mail: talbrec1@nd.ed, and Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556. 2011. "Uranyl carboxyphosphonates that incorporate Cd(II)". United States. doi:10.1016/j.jssc.2011.03.026.
@article{osti_21504073,
title = {Uranyl carboxyphosphonates that incorporate Cd(II)},
author = {Alsobrook, Andrea N. and Alekseev, Evgeny V. and Depmeier, Wulf and Albrecht-Schmitt, Thomas E., E-mail: talbrec1@nd.ed and Department of Chemistry and Biochemistry, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, IN 46556},
abstractNote = {The hydrothermal treatment of UO{sub 3}, Cd(CH{sub 3}CO{sub 2}){sub 2}.2H{sub 2}O, and triethyl phosphonoacetate results in the formation of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O (CdUPAA-1), [Cd{sub 3}(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 6}(H{sub 2}O){sub 13}].6H{sub 2}O (CdUPAA-2), and Cd(H{sub 2}O){sub 2}[(UO{sub 2})(PO{sub 3}CH{sub 2}CO{sub 2})(H{sub 2}O)]{sub 2} (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO{sub 7} pentagonal bipyramids and UO{sub 8} hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 A across that are filled with disordered water molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO{sub 7} pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together. -- Graphical abstract: A view of part of the cubic structure of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}].16H{sub 2}O. Display Omitted highlights: > High symmetry uranyl compounds. > Three-dimensional structures. > Porous materials. > Heterobimetallic compounds.},
doi = {10.1016/j.jssc.2011.03.026},
journal = {Journal of Solid State Chemistry},
number = 5,
volume = 184,
place = {United States},
year = 2011,
month = 5
}
  • The hydrothermal treatment of UO{sub 3}, Cd(CH{sub 3}CO{sub 2}){sub 2}·2H{sub 2}O, and triethyl phosphonoacetate results in the formation of Cd{sub 2}[(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 3}O{sub 3}(OH)(H{sub 2}O){sub 2}]·16H{sub 2}O (CdUPAA-1), [Cd{sub 3}(UO{sub 2}){sub 6}(PO{sub 3}CH{sub 2}CO{sub 2}){sub 6}(H{sub 2}O){sub 13}]·6H{sub 2}O (CdUPAA-2), and Cd(H{sub 2}O){sub 2}[(UO{sub 2})(PO{sub 3}CH{sub 2}CO{sub 2})(H{sub 2}O)]{sub 2} (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO{sub 7} pentagonal bipyramids and UO{sub 8} hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 Å across that are filled with disordered watermore » molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO{sub 7} pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranyl phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together.« less
  • The hydrothermal treatment of UO3, Cd(CH3CO2)2·2H2O, and triethyl phosphonoacetate results in the formation of Cd2[(UO2)6(PO3CH2CO2)3O3(OH)(H2O)2]·16H2O (CdUPAA-1), [Cd3(UO2)6(PO3CH2CO2)6(H2O)13]·6H2O (CdUPAA-2), and Cd(H2O)2[(UO2)(PO3CH2CO2)(H2O)]2 (CdUPAA-3). CdUPAA-1 adopts a cubic three-dimensional structure constructed from planar uranyl oxide clusters containing both UO7 pentagonal bipyramids and UO8 hexagonal bipyramids that are linked by Cd(II) cations and phosphonoacetate to yield large cavities approximately 16 Å across that are filled with disordered water molecules. CdUPAA-2 forms a rhombohedral three-dimensional channel structure that is assembled from UO7 pentagonal bipyramids that are bridged by phosphonoacetate. CdUPAA-3 is layered with the hydrated Cd(II) cations incorporated directly into the layers linking one-dimensional uranylmore » phosphonate substructures together. In this structure, there are complex networks of hydrogen bonds that exist within the sheets, and also stitch the sheets together.« less
  • Five heterobimetallic U(VI)/Co(II) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO 3, Co(CH 3CO 2) 2·4H 2O, and triethyl phosphonoacetate. These compounds, Co(H 2O) 4[(UO 2) 2(PO 3CH 2CO 2) 2(H 2O) 2] (CoUPAA-1), [Co(H 2O) 6][UO 2(PO 3CH 2CO 2)] 2·8H 2O (CoUPAA-2), Co(H 2O) 4[UO 2(PO 3CH 2CO 2)] 2·4H 2O (CoUPAA-3), Co(H 2O) 4[(UO 2) 62CH 2CO 2) 2O 2(OH) 3(H 2O) 3] 2·3H 2O (CoUPAA-4), and Co 2(UO 2) 6(PO 3CH 2CO 2) 3O 3(OH)(H 2O) 2·16H 2O (CoUPAA-5), range from two- to three-dimensional structures. CoUPAA-1 to CoUPAA-3 all possess uranyl carboxyphosphonate layersmore » that are separated by the Co(II) cation with varying degrees of hydration. CoUPAA-4 contains both UO 7 pentagonal bipyramids and UO 8 hexagonal bipyramids within the uranyl carboxyphosphonate plane. Unlike the first four low-symmetry compounds, CoUPAA-5 is a cubic, three-dimensional network with large cavities approximately 16 Å in diameter that are filled with cocrystallized water molecules. Differential gas absorption measurements performed on CoUPAA-5 displayed a surface area uptake for CO 2 of 40 m 2 g -1 at 273 K, and no uptake for N 2 at 77 K.« less
  • Five heterobimetallic U(VI)/M(II) (M = Mn, Fe) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO₃, triethyl phosphonoacetate, with either Mn(II) or Fe(II) acetate. The manganese reactions yield Mn₂[(UO₂)₆(PO₃CH₂CO₂)₃O₃(OH)(H₂O)₂]·16H₂O (MnUPAA-1) and [Mn(H₂O)₆][Mn(H₂O)₅Mn₂(UO₂)₅(PO₃CH₂CO₂)₆(H₂O)]·5.75H₂O (MnUPAA-2). The addition of boric acid, which lowers the crystallization temperature, allows for the production of a third product, [Mn(H₂O)₄]₂(UO₂)₃(PO₃CH₂CO₂)₂O₂ (MnUPAA-3). The iron-containing reactions yield [Fe(H₂O)₆][UO₂(PO₃CH₂CO₂)]₂·8H₂O (FeUPAA-1) and [Fe(H₂O)₆][UO₂(PO₃CH₂CO₂)H₂O]₂·4H₂O (FeUPAA-2). Four of these five compounds crystallize in low-symmetry space groups; whereas MnUPAA-1 crystallizes in the cubic space group Im3⁻ and possesses a remarkably complex open-framework structure containing both UO₇ pentagonal bipyramids and UO₈ hexagonal bipyramids. MnUPAA-3more » adopts a one-dimensional uranium oxide topology that contains both UO₆ tetragonal bipyramids and UO₇ pentagonal bipyramids. The remaining three compounds solely contain UO₇ pentagonal bipyramids.« less