Preparation of iron(IV) nitridoferrate Ca4FeN4 through azide-mediated oxidation under high-pressure conditions

Simon D. Kloß (), Arthur Haffner, Pascal Manuel, Masato Goto, Yuichi Shimakawa and J. Paul Attfield ()
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Simon D. Kloß: University of Edinburgh, Centre for Science at Extreme Conditions and School of Chemistry
Arthur Haffner: Ludwig-Maximilians-University Munich, Department Chemistry
Pascal Manuel: ISIS Neutron Source, STFC Rutherford Appleton Laboratory, Oxfordshire
Masato Goto: Kyoto University, Uji
Yuichi Shimakawa: Kyoto University, Uji
J. Paul Attfield: University of Edinburgh, Centre for Science at Extreme Conditions and School of Chemistry

Nature Communications, 2021, vol. 12, issue 1, 1-6

Abstract: Abstract Transition 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.

Date: 2021
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DOI: 10.1038/s41467-020-20881-y

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