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dc.contributor.authorHuzan, Myron S; orcid: 0000-0002-6238-3735
dc.contributor.authorFix, Manuel
dc.contributor.authorAramini, Matteo
dc.contributor.authorBencok, Peter
dc.contributor.authorMosselmans, J Frederick W; orcid: 0000-0001-6473-2743
dc.contributor.authorHayama, Shusaku
dc.contributor.authorBreitner, Franziska A
dc.contributor.authorGee, Leland B; orcid: 0000-0002-5817-3997
dc.contributor.authorTitus, Charles J; orcid: 0000-0001-6312-8552
dc.contributor.authorArrio, Marie-Anne
dc.contributor.authorJesche, Anton
dc.contributor.authorBaker, Michael L; orcid: 0000-0002-8246-3177
dc.date.accessioned2021-06-28T00:52:44Z
dc.date.available2021-06-28T00:52:44Z
dc.date.issued2020-10-07
dc.identifierpubmed: 34123206
dc.identifierdoi: 10.1039/d0sc03787g
dc.identifierpii: d0sc03787g
dc.identifierpmc: PMC8162461
dc.identifier.citationChemical science, volume 11, issue 43, page 11801-11810
dc.identifier.urihttp://hdl.handle.net/10034/625061
dc.descriptionFrom PubMed via Jisc Publications Router
dc.descriptionPublication status: epublish
dc.description.abstractLarge 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, L -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 Fe dopant ions to be linearly coordinated, occupying a 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 L -edge XAS from which the energy reduction of 3d 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 L -edge XAS can be applied to quantify the = 7/2 magnetic anisotropy barrier, 34.80 meV (∼280 cm ), that corresponds with Orbach relaxation the first excited, = ±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. [Abstract copyright: This journal is © The Royal Society of Chemistry.]
dc.languageeng
dc.sourcepissn: 2041-6520
dc.titleSingle-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy.
dc.typearticle
dc.date.updated2021-06-28T00:52:44Z


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