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

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.