Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro <i>closo</i>-Dodecaborates of 3<i>d</i> Transition Metals and of Magnesium
Magnesium and 3<i>d</i> transition metals <i>closo</i>-borates were prepared by mechanosynthesis (ball milling) of the mixtures Na<sub>2</sub>B<sub>12</sub>H<sub>12</sub> + MCl<sub>2</sub> (M = Mn, Fe, Co, Ni, Mg), followed by a...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2019-07-01
|
| Series: | Crystals |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-4352/9/7/372 |
| _version_ | 1798034564705157120 |
|---|---|
| author | Emilie Didelot Zbigniew Łodziana Fabrizio Murgia Radovan Černý |
| author_facet | Emilie Didelot Zbigniew Łodziana Fabrizio Murgia Radovan Černý |
| author_sort | Emilie Didelot |
| collection | DOAJ |
| description | Magnesium and 3<i>d</i> transition metals <i>closo</i>-borates were prepared by mechanosynthesis (ball milling) of the mixtures Na<sub>2</sub>B<sub>12</sub>H<sub>12</sub> + MCl<sub>2</sub> (M = Mn, Fe, Co, Ni, Mg), followed by addition of ethanol or methanol and drying under dynamic vacuum. The dead mass of NaCl is partly removed by filtration. The crystal structures of solvent-coordinated and solvent-free <i>closo</i>-borates have been characterized by temperature dependent synchrotron radiation X-ray powder diffraction, ab initio calculations, thermal analysis and infrared spectroscopy. Various solvated complexes containing six, four, three, two or one solvent molecules were obtained by successive removal of the solvent until in most case the solvent-free metal <i>closo</i>-borates were obtained with the exception of Mg whose hypothetical crystal structure, however, could have its prototype in MnB<sub>12</sub>H<sub>12</sub>. The 3<i>d</i> transition metal <i>closo</i>-borates were studied in the view of their potential use as Na- or Li-ion battery electrodes in combination with Na or Li <i>closo-</i>borate solid electrolytes. The metal oxidation state (II) obtained in compounds presented here does not allow such application. |
| first_indexed | 2024-04-11T20:45:59Z |
| format | Article |
| id | doaj.art-1fa4b56bee824a099905f35c296974e3 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-04-11T20:45:59Z |
| publishDate | 2019-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-1fa4b56bee824a099905f35c296974e32022-12-22T04:04:02ZengMDPI AGCrystals2073-43522019-07-019737210.3390/cryst9070372cryst9070372Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro <i>closo</i>-Dodecaborates of 3<i>d</i> Transition Metals and of MagnesiumEmilie Didelot0Zbigniew Łodziana1Fabrizio Murgia2Radovan Černý3Department of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest Ansermet 24, CH-1211 Geneva, SwitzerlandPolish Academy of Sciences, Institute of Nuclear Physics, ul. Radzikowskiego 152, 31-342 Kraków, PolandDepartment of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest Ansermet 24, CH-1211 Geneva, SwitzerlandDepartment of Quantum Matter Physics, Laboratory of Crystallography, University of Geneva, Quai Ernest Ansermet 24, CH-1211 Geneva, SwitzerlandMagnesium and 3<i>d</i> transition metals <i>closo</i>-borates were prepared by mechanosynthesis (ball milling) of the mixtures Na<sub>2</sub>B<sub>12</sub>H<sub>12</sub> + MCl<sub>2</sub> (M = Mn, Fe, Co, Ni, Mg), followed by addition of ethanol or methanol and drying under dynamic vacuum. The dead mass of NaCl is partly removed by filtration. The crystal structures of solvent-coordinated and solvent-free <i>closo</i>-borates have been characterized by temperature dependent synchrotron radiation X-ray powder diffraction, ab initio calculations, thermal analysis and infrared spectroscopy. Various solvated complexes containing six, four, three, two or one solvent molecules were obtained by successive removal of the solvent until in most case the solvent-free metal <i>closo</i>-borates were obtained with the exception of Mg whose hypothetical crystal structure, however, could have its prototype in MnB<sub>12</sub>H<sub>12</sub>. The 3<i>d</i> transition metal <i>closo</i>-borates were studied in the view of their potential use as Na- or Li-ion battery electrodes in combination with Na or Li <i>closo-</i>borate solid electrolytes. The metal oxidation state (II) obtained in compounds presented here does not allow such application.https://www.mdpi.com/2073-4352/9/7/372<i>Closo</i>-boratetransition metalethanol complexmethanol complexX-ray powder diffraction |
| spellingShingle | Emilie Didelot Zbigniew Łodziana Fabrizio Murgia Radovan Černý Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro <i>closo</i>-Dodecaborates of 3<i>d</i> Transition Metals and of Magnesium Crystals <i>Closo</i>-borate transition metal ethanol complex methanol complex X-ray powder diffraction |
| title | Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro <i>closo</i>-Dodecaborates of 3<i>d</i> Transition Metals and of Magnesium |
| title_full | Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro <i>closo</i>-Dodecaborates of 3<i>d</i> Transition Metals and of Magnesium |
| title_fullStr | Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro <i>closo</i>-Dodecaborates of 3<i>d</i> Transition Metals and of Magnesium |
| title_full_unstemmed | Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro <i>closo</i>-Dodecaborates of 3<i>d</i> Transition Metals and of Magnesium |
| title_short | Ethanol- and Methanol-Coordinated and Solvent-Free Dodecahydro <i>closo</i>-Dodecaborates of 3<i>d</i> Transition Metals and of Magnesium |
| title_sort | ethanol and methanol coordinated and solvent free dodecahydro i closo i dodecaborates of 3 i d i transition metals and of magnesium |
| topic | <i>Closo</i>-borate transition metal ethanol complex methanol complex X-ray powder diffraction |
| url | https://www.mdpi.com/2073-4352/9/7/372 |
| work_keys_str_mv | AT emiliedidelot ethanolandmethanolcoordinatedandsolventfreedodecahydroiclosoidodecaboratesof3iditransitionmetalsandofmagnesium AT zbigniewłodziana ethanolandmethanolcoordinatedandsolventfreedodecahydroiclosoidodecaboratesof3iditransitionmetalsandofmagnesium AT fabriziomurgia ethanolandmethanolcoordinatedandsolventfreedodecahydroiclosoidodecaboratesof3iditransitionmetalsandofmagnesium AT radovancerny ethanolandmethanolcoordinatedandsolventfreedodecahydroiclosoidodecaboratesof3iditransitionmetalsandofmagnesium |