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Copper(II) perrhenate Cu(C3H7OH)2(ReO4)2: Synthesis from isopropanol and CuReO4, structure and properties

Mikhailova, D. and Engel, J. M. and Schmidt, M. and Tsirlin, A. A. and Ehrenberg, H. (2015):
Copper(II) perrhenate Cu(C3H7OH)2(ReO4)2: Synthesis from isopropanol and CuReO4, structure and properties.
In: Journal of Solid State Chemistry, 232Elsevier Science Publishing, pp. 264-269, ISSN 00224596,
[Online-Edition: http://dx.doi.org/10.1016/j.jssc.2015.08.042],
[Article]

Abstract

The crystal structure of Cu+Re7+O4 is capable of a quasi-reversible incorporation of C3H7OH molecules. A room-temperature reaction between CuReO4 and C3H7OH under oxidizing conditions leads to the formation of a novel metal-organic hybrid compound Cu2+(C3H7OH)2(ReO4)2. Upon heating under reducing conditions, this compound transforms back into CuReO4, albeit with ReO2 and metallic Cu as by-products. The crystal structure of Cu(C3H7OH)2(ReO4)2 solved from single-crystal X-ray diffraction (Pbca, a=10.005(3) Å, b=7.833(2) Å, and c=19.180(5) Å) reveals layers of corner-sharing CuO6-octahedra and ReO4-tetrahedra, whereas isopropyl groups are attached to both sides of these layers, thus providing additional connections within the layers through hydrogen bonds. Cu(C3H7OH)2(ReO4)2 is paramagnetic down to 4 K because the spatial arrangement of the Cu2+ half-filled orbitals prevents magnetic superexchange. The paramagnetic effective moment of 2.0(1) μB is slightly above the spin-only value and typical for Cu2+ ions.

Item Type: Article
Erschienen: 2015
Creators: Mikhailova, D. and Engel, J. M. and Schmidt, M. and Tsirlin, A. A. and Ehrenberg, H.
Title: Copper(II) perrhenate Cu(C3H7OH)2(ReO4)2: Synthesis from isopropanol and CuReO4, structure and properties
Language: English
Abstract:

The crystal structure of Cu+Re7+O4 is capable of a quasi-reversible incorporation of C3H7OH molecules. A room-temperature reaction between CuReO4 and C3H7OH under oxidizing conditions leads to the formation of a novel metal-organic hybrid compound Cu2+(C3H7OH)2(ReO4)2. Upon heating under reducing conditions, this compound transforms back into CuReO4, albeit with ReO2 and metallic Cu as by-products. The crystal structure of Cu(C3H7OH)2(ReO4)2 solved from single-crystal X-ray diffraction (Pbca, a=10.005(3) Å, b=7.833(2) Å, and c=19.180(5) Å) reveals layers of corner-sharing CuO6-octahedra and ReO4-tetrahedra, whereas isopropyl groups are attached to both sides of these layers, thus providing additional connections within the layers through hydrogen bonds. Cu(C3H7OH)2(ReO4)2 is paramagnetic down to 4 K because the spatial arrangement of the Cu2+ half-filled orbitals prevents magnetic superexchange. The paramagnetic effective moment of 2.0(1) μB is slightly above the spin-only value and typical for Cu2+ ions.

Journal or Publication Title: Journal of Solid State Chemistry
Volume: 232
Publisher: Elsevier Science Publishing
Uncontrolled Keywords: Metal-organic framework, Jahn–Teller distortion of CuO6 octahedra, Hydrogen bonds
Divisions: 11 Department of Materials and Earth Sciences > Material Science > Structure Research
11 Department of Materials and Earth Sciences > Material Science
11 Department of Materials and Earth Sciences
Date Deposited: 29 Oct 2015 09:49
Official URL: http://dx.doi.org/10.1016/j.jssc.2015.08.042
Identification Number: doi:10.1016/j.jssc.2015.08.042
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