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Title: Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth

Abstract

The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y{sup 3+} is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH{sub 4} both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A{sub 3}Y(BH{sub 4}){sub 6} or c-A{sub 2}LiY(BH{sub 4}){sub 6} (A=Rb, Cs) form in all the investigated systems, with the exception of the Li–K–Y system. The compounds with the stoichiometry AY(BH{sub 4}){sub 4} crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride – closo-borane is observed during decomposition of all double perovskites. - Graphical abstract: The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five novel compounds and four further ones previously reported. Significant coordination flexibility of Y{sup 3+} is revealed, which can be employed to form both octahedral frameworks and tetrahedralmore » complex anions, very different structural topologies. Versatility is also manifested in three different simultaneously occurring coordination modes of borohydrides for one metal cation, as proposed by DFT optimization of the monoclinic KY(BH{sub 4}){sub 4} structural model observed by powder diffraction. - Highlights: • The system Li-A-Y-BH{sub 4} (A=K, Rb, Cs) contains nine compounds in total. • Y{sup 3+} forms octahedral frameworks and tetrahedral complex anions. • Bi- and trimetallic double-perovskites crystallize in most systems. • Various AY(BH{sub 4}){sub 4} crystallize with structure types analogous to metal oxides. • Double-perovskites decompose and form a novel borohydride-closo-borane.« less

Authors:
 [1];  [1];  [1]; ;  [2];  [3];  [1]
  1. Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest-Ansermet 24, CH-1211 Geneva (Switzerland)
  2. Center for Materials Crystallography (CMC), Interdisciplinary Nanoscience Center (iNANO), and Department of Chemistry, Aarhus University, Langelandsgade 140, DK-8000 Århus C (Denmark)
  3. Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana (Slovenia)
Publication Date:
OSTI Identifier:
22475599
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 225; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; BOROHYDRIDES; BORON HYDRIDES; CATIONS; CESIUM COMPOUNDS; DECOMPOSITION; FLEXIBILITY; LIGANDS; LITHIUM COMPOUNDS; MONOCLINIC LATTICES; OPTIMIZATION; PHASE STABILITY; POWDERS; RUBIDIUM COMPOUNDS; STOICHIOMETRY; STRUCTURAL MODELS; X-RAY DIFFRACTION; YTTRIUM IONS

Citation Formats

Sadikin, Yolanda, Stare, Katarina, Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana, Schouwink, Pascal, Brix Ley, Morten, Jensen, Torben R., Meden, Anton, and Černý, Radovan. Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth. United States: N. p., 2015. Web. doi:10.1016/J.JSSC.2014.12.018.
Sadikin, Yolanda, Stare, Katarina, Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana, Schouwink, Pascal, Brix Ley, Morten, Jensen, Torben R., Meden, Anton, & Černý, Radovan. Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth. United States. https://doi.org/10.1016/J.JSSC.2014.12.018
Sadikin, Yolanda, Stare, Katarina, Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana, Schouwink, Pascal, Brix Ley, Morten, Jensen, Torben R., Meden, Anton, and Černý, Radovan. 2015. "Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth". United States. https://doi.org/10.1016/J.JSSC.2014.12.018.
@article{osti_22475599,
title = {Alkali metal – yttrium borohydrides: The link between coordination of small and large rare-earth},
author = {Sadikin, Yolanda and Stare, Katarina and Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerjeva 5, SI-1000 Ljubljana and Schouwink, Pascal and Brix Ley, Morten and Jensen, Torben R. and Meden, Anton and Černý, Radovan},
abstractNote = {The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five new compounds and four further ones known from previous work on the homoleptic borohydrides. Crystal structures have been solved and refined from synchrotron X-ray powder diffraction, thermal stability of new compounds have been investigated and ionic conductivity measured for selected samples. Significant coordination flexibility for Y{sup 3+} is revealed, which allows the formation of both octahedral frameworks and tetrahedral complex anions with the tetrahydroborate anion BH{sub 4} both as a linker and terminal ligand. Bi- and trimetallic cubic double-perovskites c-A{sub 3}Y(BH{sub 4}){sub 6} or c-A{sub 2}LiY(BH{sub 4}){sub 6} (A=Rb, Cs) form in all the investigated systems, with the exception of the Li–K–Y system. The compounds with the stoichiometry AY(BH{sub 4}){sub 4} crystallize in all investigated systems with a great variety of structure types which find their analog amongst metal oxides. In-situ formation of a new borohydride – closo-borane is observed during decomposition of all double perovskites. - Graphical abstract: The system Li–A–Y–BH{sub 4} (A=K, Rb, Cs) is found to contain five novel compounds and four further ones previously reported. Significant coordination flexibility of Y{sup 3+} is revealed, which can be employed to form both octahedral frameworks and tetrahedral complex anions, very different structural topologies. Versatility is also manifested in three different simultaneously occurring coordination modes of borohydrides for one metal cation, as proposed by DFT optimization of the monoclinic KY(BH{sub 4}){sub 4} structural model observed by powder diffraction. - Highlights: • The system Li-A-Y-BH{sub 4} (A=K, Rb, Cs) contains nine compounds in total. • Y{sup 3+} forms octahedral frameworks and tetrahedral complex anions. • Bi- and trimetallic double-perovskites crystallize in most systems. • Various AY(BH{sub 4}){sub 4} crystallize with structure types analogous to metal oxides. • Double-perovskites decompose and form a novel borohydride-closo-borane.},
doi = {10.1016/J.JSSC.2014.12.018},
url = {https://www.osti.gov/biblio/22475599}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 225,
place = {United States},
year = {Fri May 15 00:00:00 EDT 2015},
month = {Fri May 15 00:00:00 EDT 2015}
}