Wu, Shijun, Kowalski, Piotr M., Yu, Na, Malcherek, Thomas, Depmeier, Wulf, Bosbach, Dirk, Wang, Shuao, Suleimanov, Evgeny V., Albrecht-Schmitt, Thomas E. and Alekseev, Evgeny V. (2014) Highly Distorted Uranyl Ion Coordination and One/Two-Dimensional Structural Relationship in the Ba-2 UO2(TO4)(2) (T = P, As) System: An Experimental and Computational Study. Inorganic Chemistry, 53 (14). pp. 7650-7660. DOI 10.1021/ic500965v.

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Abstract

Uranium compounds alpha-Ba-2[UO2(PO4)(2)] (1), beta-Ba-2[UO2(PO4)(2)] (2), and Ba-2[UO2(AsO4)(2)] (3) were synthesized by H3BO3/B2O3 flux reactions, though boron is not incorporated into the structures. Phases I 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 I 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 beta-Ba-2[UO2(PO4)(2)] and Ba-2[UO2(AsO4)(2)] indicate a possible evolution of uranyl-based structures from chain to layer type and formation of an accretional series.

Document Type:	Article
Additional Information:	Times Cited: 0 Wu, Shijun/B-1016-2010; Malcherek, Thomas/M-1424-2014 Wu, Shijun/0000-0003-0343-3322; 0
Research affiliation:	Kiel University Kiel University > Kiel Marine Science
Refereed:	Yes
Open Access Journal?:	No
Publisher:	American Chemical Society
Projects:	Future Ocean
Date Deposited:	30 Mar 2015 12:53
Last Modified:	23 Sep 2019 21:45
URI:	https://oceanrep.geomar.de/id/eprint/28352

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