The Flexible Ba 7 UM 2 S 12.5 O 0.5 (M = V, Fe) Compounds: Syntheses, Structures and Spectroscopic, Resistivity, and Electronic Properties

Abstract : Two new compounds, Ba7UV2S12.5O0.5 and Ba7UFe2S12.5O0.5, have been synthesized in fused-silica tubes by the direct combinations of V or Fe with U, BaS, and S at 1223 K. The compound Ba7UV2S12.5O0.5 crystallizes at 100 K in the Cs7Cd3Br17 structure type in space group D4h18–I4/mcm of the tetragonal system. The compound Ba7UFe2S12.5O0.5 crystallizes at 100 K in space group D4h5–P4/mbm of the tetragonal system. The structures are very similar with V/S or Fe/S networks in which Ba atoms reside as well as channels large enough to accommodate additional Ba atoms and infinite linear US5O chains. Each U atom is octahedrally coordinated to four equatorial S atoms, one axial S atom, and one axial O atom. The Fe/S network contains a S–S single bond, whereas the V/S network does not. The result is that the Fe3+ compound charge balances with 7 Ba2+, U4+, 2 Fe3+, 10.5 S2–, S22–, and 0.5 O2–, whereas the V4+ compound charge balances with 7 Ba2+, U4+, 2 V4+, 12.5 S2–, and 0.5 O2–. Other differences between these two compounds have been characterized by Raman spectroscopy and resistivity measurements. DFT calculations have provided insight into the nature of their bonding. The overall structural motif of Ba7UV2S12.5O0.5 and Ba7UFe2S12.5O0.5 offers a remarkable flexibility in terms of the oxidation state of the incorporated transition metal.
Type de document :
Article dans une revue
Inorganic Chemistry, American Chemical Society, 2013, 52 (20), pp.12057 - 12063. 〈10.1021/ic401871x〉
Liste complète des métadonnées

https://hal.univ-lorraine.fr/hal-01521971
Contributeur : Crm2 Ul <>
Soumis le : vendredi 12 mai 2017 - 15:42:39
Dernière modification le : mercredi 31 janvier 2018 - 12:14:44

Identifiants

Citation

Adel Mesbah, Wojciech Stojko, Christos D. Malliakas, Sébastien Lebègue, Nicolas Clavier, et al.. The Flexible Ba 7 UM 2 S 12.5 O 0.5 (M = V, Fe) Compounds: Syntheses, Structures and Spectroscopic, Resistivity, and Electronic Properties. Inorganic Chemistry, American Chemical Society, 2013, 52 (20), pp.12057 - 12063. 〈10.1021/ic401871x〉. 〈hal-01521971〉

Partager

Métriques

Consultations de la notice

120