Syntheses, structures, and comparisons of thallium uranium phosphites, mixed phosphate-phosphites, and phosphate

Eric Villa; Evgeny V. Alekseev; Wulf Depmeier; Thomas E. Albrecht-Schmitt

doi:10.1021/cg400046a

Syntheses, structures, and comparisons of thallium uranium phosphites, mixed phosphate-phosphites, and phosphate

Eric Villa, Evgeny V. Alekseev, Wulf Depmeier, Thomas E. Albrecht-Schmitt

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19 Scopus citations

Abstract

A new family of six thallium uranium phosphites and phosphates has been synthesized. Here there are three new thallium uranyl phosphites, Tl ₂[(UO₂)(HPO₃)(H₂PO ₃)]₂1, Tl₂[(UO₂) ₂(HPO₃)₃]·H₂O 2, and Tl ₆[(UO₂)₅(H₂O)(HPO₃) ₈]·2H₂O 3, a uranyl phosphate-phosphite, Tl ₃[(UO₂)₂(H_1.5PO₄)(H _0.5PO₄)(H_1.5PO₃)₂] 4, a mixed uranium(VI)-uranium(IV) phosphate-phosphite, Tl₂[(UO ₂)₂(U^IV)(H₂O)(PO₄) ₂(HPO₃)₂] 5, and, finally, a thallium uranium(IV) phosphate, Tl₂[U^IV(PO₄) ₂] 6, which were hydrothermally synthesized using thallium carbonate, uranyl nitrate, and H₃PO₃ as initial reagents. The above phases were all isolated from mixtures and were characterized by single-crystal X-ray diffraction and solid-state UV-vis-NIR spectroscopy. Compounds 1, 2, 3, and 5 are isotypic to known topologies. Herein, we investigate these six new thallium compounds and explore the effects of the thallium carbonate concentration and time on the reduction of uranium, via the phosphite ligand, within the crystalline products observed and also examine how these thallium species relate in terms of unit cells, symmetry, and bonding to known uranium phases.

Original language	English
Pages (from-to)	1721-1729
Number of pages	9
Journal	Crystal Growth and Design
Volume	13
Issue number	4
DOIs	https://doi.org/10.1021/cg400046a
Publication status	Published - Apr 3 2013
Externally published	Yes

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All Science Journal Classification (ASJC) codes

Chemistry(all)
Materials Science(all)
Condensed Matter Physics

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Villa, E., Alekseev, E. V., Depmeier, W., & Albrecht-Schmitt, T. E. (2013). Syntheses, structures, and comparisons of thallium uranium phosphites, mixed phosphate-phosphites, and phosphate. Crystal Growth and Design, 13(4), 1721-1729. https://doi.org/10.1021/cg400046a

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abstract = "A new family of six thallium uranium phosphites and phosphates has been synthesized. Here there are three new thallium uranyl phosphites, Tl 2[(UO2)(HPO3)(H2PO 3)]21, Tl2[(UO2) 2(HPO3)3]·H2O 2, and Tl 6[(UO2)5(H2O)(HPO3) 8]·2H2O 3, a uranyl phosphate-phosphite, Tl 3[(UO2)2(H1.5PO4)(H 0.5PO4)(H1.5PO3)2] 4, a mixed uranium(VI)-uranium(IV) phosphate-phosphite, Tl2[(UO 2)2(UIV)(H2O)(PO4) 2(HPO3)2] 5, and, finally, a thallium uranium(IV) phosphate, Tl2[UIV(PO4) 2] 6, which were hydrothermally synthesized using thallium carbonate, uranyl nitrate, and H3PO3 as initial reagents. The above phases were all isolated from mixtures and were characterized by single-crystal X-ray diffraction and solid-state UV-vis-NIR spectroscopy. Compounds 1, 2, 3, and 5 are isotypic to known topologies. Herein, we investigate these six new thallium compounds and explore the effects of the thallium carbonate concentration and time on the reduction of uranium, via the phosphite ligand, within the crystalline products observed and also examine how these thallium species relate in terms of unit cells, symmetry, and bonding to known uranium phases.",

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AU - Villa, Eric

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N2 - A new family of six thallium uranium phosphites and phosphates has been synthesized. Here there are three new thallium uranyl phosphites, Tl 2[(UO2)(HPO3)(H2PO 3)]21, Tl2[(UO2) 2(HPO3)3]·H2O 2, and Tl 6[(UO2)5(H2O)(HPO3) 8]·2H2O 3, a uranyl phosphate-phosphite, Tl 3[(UO2)2(H1.5PO4)(H 0.5PO4)(H1.5PO3)2] 4, a mixed uranium(VI)-uranium(IV) phosphate-phosphite, Tl2[(UO 2)2(UIV)(H2O)(PO4) 2(HPO3)2] 5, and, finally, a thallium uranium(IV) phosphate, Tl2[UIV(PO4) 2] 6, which were hydrothermally synthesized using thallium carbonate, uranyl nitrate, and H3PO3 as initial reagents. The above phases were all isolated from mixtures and were characterized by single-crystal X-ray diffraction and solid-state UV-vis-NIR spectroscopy. Compounds 1, 2, 3, and 5 are isotypic to known topologies. Herein, we investigate these six new thallium compounds and explore the effects of the thallium carbonate concentration and time on the reduction of uranium, via the phosphite ligand, within the crystalline products observed and also examine how these thallium species relate in terms of unit cells, symmetry, and bonding to known uranium phases.

AB - A new family of six thallium uranium phosphites and phosphates has been synthesized. Here there are three new thallium uranyl phosphites, Tl 2[(UO2)(HPO3)(H2PO 3)]21, Tl2[(UO2) 2(HPO3)3]·H2O 2, and Tl 6[(UO2)5(H2O)(HPO3) 8]·2H2O 3, a uranyl phosphate-phosphite, Tl 3[(UO2)2(H1.5PO4)(H 0.5PO4)(H1.5PO3)2] 4, a mixed uranium(VI)-uranium(IV) phosphate-phosphite, Tl2[(UO 2)2(UIV)(H2O)(PO4) 2(HPO3)2] 5, and, finally, a thallium uranium(IV) phosphate, Tl2[UIV(PO4) 2] 6, which were hydrothermally synthesized using thallium carbonate, uranyl nitrate, and H3PO3 as initial reagents. The above phases were all isolated from mixtures and were characterized by single-crystal X-ray diffraction and solid-state UV-vis-NIR spectroscopy. Compounds 1, 2, 3, and 5 are isotypic to known topologies. Herein, we investigate these six new thallium compounds and explore the effects of the thallium carbonate concentration and time on the reduction of uranium, via the phosphite ligand, within the crystalline products observed and also examine how these thallium species relate in terms of unit cells, symmetry, and bonding to known uranium phases.

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10.1021/cg400046a