This title appears in the Scientific Report :
2014
Please use the identifier:
http://dx.doi.org/10.1021/ic500965v in citations.
Highly Distorted Uranyl Ion Coordination and One/Two-Dimensional Structural Relationship in the Ba2[UO2(TO4)2] (T = P, As) System: An Experimental and Computational Study
Highly Distorted Uranyl Ion Coordination and One/Two-Dimensional Structural Relationship in the Ba2[UO2(TO4)2] (T = P, As) System: An Experimental and Computational Study
Uranium compounds α-Ba2[UO2(PO4)2] (1), β-Ba2[UO2(PO4)2] (2), and Ba2[UO2(AsO4)2] (3) were synthesized by H3BO3/B2O3 flux reactions, though boron is not incorporated into the structures. Phases 1 and 2 are topologically identical, but 1 is heavily distorted with respect to 2. An unusual UO7 pentagon...
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Personal Name(s): | Wu, Shijun |
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Kowalski, Piotr / Yu, Na / Malcherek, Thomas / Depmeier, Wulf / Bosbach, Dirk / Wang, Shuao / Suleimanov, Evgeny V. / Albrecht-Schmitt, Thomas E. / Alekseev, Evgeny (Corresponding Author) | |
Contributing Institute: |
Nukleare Entsorgung; IEK-6 |
Published in: | Inorganic chemistry, 53 (2014) 14, S. 7650 - 7660 |
Imprint: |
Washington, DC
American Chemical Society
2014
|
PubMed ID: |
24991981 |
DOI: |
10.1021/ic500965v |
Document Type: |
Journal Article |
Research Program: |
Helmholtz Interdisciplinary Doctoral Training in Energy and Climate Research (HITEC) Safety Research for Nuclear Waste Disposal |
Publikationsportal JuSER |
Uranium compounds α-Ba2[UO2(PO4)2] (1), β-Ba2[UO2(PO4)2] (2), and Ba2[UO2(AsO4)2] (3) were synthesized by H3BO3/B2O3 flux reactions, though boron is not incorporated into the structures. Phases 1 and 2 are topologically identical, but 1 is heavily distorted with respect to 2. An unusual UO7 pentagonal bipyramid occurs in 1, exhibiting a highly distorted equatorial configuration and significant bending of the uranyl group, due to edge-sharing with one neighboring PO43– tetrahedron. Compound 2 contains more normal square bipyramids that share corners with four neighboring PO43– tetrahedra, but the uranyl cation UO22+ is tilted relative to the equatorial plane. Experimental evidence as well as density functional theory (DFT) calculations suggest that 1 is more stable than 2. In theory, 1 and 2 can interconvert by forming/releasing the shared edge between the uranyl polyhedron and the phosphate tetrahedron. Similar fundamental building blocks in β-Ba2[UO2(PO4)2] and Ba2[UO2(AsO4)2] indicate a possible evolution of uranyl-based structures from chain to layer type and formation of an accretional series. |