Kloß Simon D, Haffner Arthur, Manuel Pascal, Goto Masato, Shimakawa Yuichi, Attfield J Paul
University of Edinburgh, Centre for Science at Extreme Conditions and School of Chemistry, Edinburgh, EH9 3FD, UK.
Ludwig-Maximilians-University Munich, Department Chemistry, 81377, Munich, Germany.
Nat Commun. 2021 Jan 25;12(1):571. doi: 10.1038/s41467-020-20881-y.
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 CaFeN containing Fe ions. This nitridometallate features trigonal-planar [FeN] anions with low-spin Fe and antiferromagnetic ordering below a Neel temperature of 25 K, which are characterised by neutron diffraction, Fe-Mössbauer and magnetisation measurements. Azide-mediated high-pressure synthesis opens a way to the discovery of highly oxidised nitrides.
过渡金属氮化物是一类重要的材料，可用作磨料、半导体、超导体、锂离子导体和热电材料。然而，由于二氮的氧化电位受到其高热力学稳定性和化学惰性的限制，高氧化态难以实现。在此，我们展示了一种在压力下使用叠氮介导氧化的通用合成路线，该路线用于制备含有铁离子的高氧化态三元氮化物CaFeN。这种氮金属酸盐具有三角平面[FeN]阴离子，其中铁为低自旋且在25 K的尼尔温度以下具有反铁磁有序，这通过中子衍射、铁-穆斯堡尔谱和磁化测量进行了表征。叠氮介导的高压合成开辟了发现高氧化态氮化物的途径。
