Abstract
AbstractTransition metal nitrides are an important class of materials with applications as abrasives, semiconductors, superconductors, Li-ion conductors, and thermoelectrics. However, high oxidation states are difficult to attain as the oxidative potential of dinitrogen is limited by its high thermodynamic stability and chemical inertness. Here we present a versatile synthesis route using azide-mediated oxidation under pressure that is used to prepare the highly oxidised ternary nitride Ca4FeN4 containing Fe4+ ions. This nitridometallate features trigonal-planar [FeN3]5− anions with low-spin Fe4+ and antiferromagnetic ordering below a Neel temperature of 25 K, which are characterised by neutron diffraction, 57Fe-Mössbauer and magnetisation measurements. Azide-mediated high-pressure synthesis opens a way to the discovery of highly oxidised nitrides.
Funder
RCUK | Engineering and Physical Sciences Research Council
Publisher
Springer Science and Business Media LLC
Subject
General Physics and Astronomy,General Biochemistry, Genetics and Molecular Biology,General Chemistry
Reference57 articles.
1. Jørgensen, C. K. New understanding of unusual oxidation states in the transition groups. Naturwissenschaften 63, 292–292 (1976).
2. Riedel, S. & Kaupp, M. The highest oxidation states of the transition metal elements. Coord. Chem. Rev. 253, 606–624 (2009).
3. Malchus, M. & Jansen, M. Kombination von Ionenaustausch und Gefriertrocknung als Syntheseweg zu neuen Oxoferraten(VI) M2FeO4 mit M = Li, Na, N(CH3)4, N(CH3)3Bzl, N(CH3)3Ph. Z. Anorg. Allg. Chem. 624, 1846–1854 (1998).
4. Harnischmacher, W. & Hoppe, R. Tetravalent copper: Cs2[CuF6]. Angew. Chem. Int. Ed. Engl. 12, 582–583 (1973).
5. Frankenburger, W., Andrussow, L. & Dürr, F. Eine neue Komplexverbindung von Lithium, Eisen und Stickstoff. Ein Beitrag zur Frage der Stickstoffbindung an Eisen. Z. Elektrochem. Angew. Phys. Chem. 34, 632–637 (1928).
Cited by
15 articles.
订阅此论文施引文献
订阅此论文施引文献，注册后可以免费订阅5篇论文的施引文献，订阅后可以查看论文全部施引文献