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Issue 43, 2020
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Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy

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Abstract

Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L2,3-edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine FeI dopant ions to be linearly coordinated, occupying a D6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L2,3-edge XAS from which the energy reduction of 3dz2 due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L3-edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (∼280 cm−1), that corresponds with Orbach relaxation via the first excited, MJ = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.

Graphical abstract: Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy

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Supplementary files

Article information


Submitted
10 Jul 2020
Accepted
02 Oct 2020
First published
07 Oct 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 11801-11810
Article type
Edge Article

Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy

M. S. Huzan, M. Fix, M. Aramini, P. Bencok, J. F. W. Mosselmans, S. Hayama, F. A. Breitner, L. B. Gee, C. J. Titus, M. Arrio, A. Jesche and M. L. Baker, Chem. Sci., 2020, 11, 11801 DOI: 10.1039/D0SC03787G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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