Synthesis, characterization, and crystal structures of uranyl compounds containing mixed chromium oxidation states
- Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, University of Notre Dame, Notre Dame, IN 46556 (United States)
- Radiation Laboratory, University of Notre Dame, Notre Dame, IN 46556 (United States)
The mixed-valence chromium uranyl compounds Li{sub 5}[(UO{sub 2}){sub 4}(Cr(V)O{sub 5})(Cr(VI)O{sub 4}){sub 4}](H{sub 2}O){sub 17} (1), (Mg(H{sub 2}O){sub 6}){sub 5}[(UO{sub 2}){sub 8}(Cr(V)O{sub 5}){sub 2}(Cr(VI)O{sub 4}){sub 8}] (2) and (NH{sub 4}){sub 5}[(UO{sub 2}){sub 4}(Cr(V)O{sub 5})(Cr(VI)O{sub 4}){sub 2}]H{sub 2}O{sub 11} (3) have been synthesized and characterized. Each contains an identical sheet of cation-centered polyhedra. Central to the connectivity of the sheet are four uranyl pentagonal bipyramids that share some of their equatorial vertices, giving a four-membered ring. The Cr(V) cation located near the center of this ring is coordinated by O atoms in a square pyramidal arrangement. The Cr(VI) is tetrahedrally coordinated by O atoms, and these tetrahedra link the four-membered rings of bipyramids. The mixed-valence nature of the sheet was verified by XANES, an EPR spectrum, and bond-valence analysis. Low-valence cations and H{sub 2}O groups reside between the sheets of uranyl and chromate polyhedra, where they provide linkages between adjacent sheets. - Graphical abstract: Three uranyl chromate compounds contain both pentavalent and hexavalent chromium. The unusual topology of the uranyl chromate sheet contains unusual pentavalent chromium in a square pyramidal coordination environment. Highlights: Black-Right-Pointing-Pointer The first uranyl compounds with mixed Cr valences are reported. Black-Right-Pointing-Pointer A sheet of uranyl polyhedra stabilizes pentavalent chromium. Black-Right-Pointing-Pointer Uranyl and chromate polyhedra form a topologically novel sheet.
- OSTI ID:
- 22012187
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. . 191; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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