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; J. Paul Attfield

doi:10.1038/s41467-020-20881-y

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, J. Paul Attfield

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract / Description of output

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.

Original language	English
Article number	571
Number of pages	6
Journal	Nature Communications
Volume	12
Issue number	1
Early online date	25 Jan 2021
DOIs	https://doi.org/10.1038/s41467-020-20881-y
Publication status	E-pub ahead of print - 25 Jan 2021

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20210303_Attfield_s41467-020-20881-yFinal published version, 1.12 MBLicence: Creative Commons: Attribution (CC-BY)

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

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-M{\"o}ssbauer and magnetisation measurements. Azide-mediated high-pressure synthesis opens a way to the discovery of highly oxidised nitrides.",

author = "Klo{\ss}, {Simon D.} and Arthur Haffner and Pascal Manuel and Masato Goto and Yuichi Shimakawa and Attfield, {J. Paul}",

note = "Funding Information: The authors gratefully acknowledge Dr. Tobias Rackl (LMU Munich) for PPMS measurements. Funding was provided by a DFG research fellowship for Dr. S. D. Klo{\ss} and EPSRC and access to the ISIS facility is through STFC. Publisher Copyright: {\textcopyright} 2021, Crown. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

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doi = "10.1038/s41467-020-20881-y",

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AU - Kloß, Simon D.

AU - Haffner, Arthur

AU - Manuel, Pascal

AU - Goto, Masato

AU - Shimakawa, Yuichi

AU - Attfield, J. Paul

N1 - Funding Information: The authors gratefully acknowledge Dr. Tobias Rackl (LMU Munich) for PPMS measurements. Funding was provided by a DFG research fellowship for Dr. S. D. Kloß and EPSRC and access to the ISIS facility is through STFC. Publisher Copyright: © 2021, Crown. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/1/25

Y1 - 2021/1/25

N2 - 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.

AB - 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.

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DO - 10.1038/s41467-020-20881-y

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AN - SCOPUS:85099993093

SN - 2041-1723

VL - 12

JO - Nature Communications

JF - Nature Communications

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M1 - 571

ER -

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

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