Structure · dataset · 2026
Probing Magnetic Anisotropy in (NBu<sup>n</sup><sub>4</sub>)<sub>2</sub>[ReX<sub>6</sub>] (X = Cl, Br, I): Ligand Field of the Re<sup>IV</sup>-Halide Bonds in Distorted Octahedral Complexes
Listed in Loughborough Research Repository and GRANTS Data and UP Research Data Repository — shown once because both records carry DOI 10.1021/acs.inorgchem.6c04158.s001
In six-coordinate complexes with <i>S</i> ≥ 1, deviations from perfect <i>O</i><sub><i>h</i></sub> geometry lead to magnetic anisotropy.
Description
We have studied (NBu<sup>n</sup><sub>4</sub>)<sub>2</sub>[Re<sup>IV</sup>X<sub>6</sub>] (<b>Re–X</b>; X = Cl, Br, I; <i>S</i> = 3/2), including zero-field splitting (ZFS) in <b>Re–I,</b> by advanced spectroscopies [far-IR magneto-spectroscopy (FIRMS), high-frequency and -field EPR (HFEPR), and inelastic neutron scattering (INS)].
AC susceptibility of <b>Re–I</b> shows field-induced SMM (single-molecule magnet) properties. Unlike <b>Re–I</b> with one unique [ReI<sub>6</sub>]<sup>2–</sup> center, there are four and three different [ReX<sub>6</sub>]<sup>2–</sup> centers in the crystallographic unit cells of <b>Re–Cl</b> and <b>Re–Br</b>, respectively. <i>Ab initio</i> calculations determine ZFS parameters and show that magnetic anisotropies are influenced by deviations from the <i>O</i><sub><i>h</i></sub> geometry and by increased covalency from <b>Re–Cl</b> to <b>Re–Br</b> to <b>Re–I</b>.
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Although Re–X bond lengths increase from <b>Re–Cl</b> to <b>Re–Br</b> to <b>Re–I</b>, the calculations reveal that the longer Re–I bonds are compensated by the diffuse, better-overlapping orbitals of I<sup>–</sup> ligands. The diffuseness in ligand orbitals likely contributes to the SMM performance of <b>Re–I</b>. The calculations also indicate that deviations from the <i>O</i><sub><i>h</i></sub> geometry in [ReX<sub>6</sub>]<sup>2–</sup> ions are the sole source of magnetic anisotropy and that there is no heavy-atom effect from the halide ligands.
Spin-phonon couplings in <b>Re–I</b> have been probed by FIRMS using results from DFT phonon calculations.
Links
Where it is published
- DOI doi.org/10.1021/acs.inorgchem.6c04158.s001 ↗
DOI / persistent id · from repository lboro ac uk
Catalogue records · 1
- OAI-PMH record api.figshare.com/v2/oai?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai%3Af… ↗
metadata API · from repository lboro ac uk
Topics
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- Inferred from text
- Density functional theory 65%
Provenance · 3 source records, 40 field assertions
| Source | Key | Last seen | Raw |
|---|---|---|---|
| Loughborough Research Repository | oai:figshare.com:article/34057060 | 4 d ago | JSON v1 |
| GRANTS Data | oai:figshare.com:article/34057060 | 4 d ago | JSON v1 |
| UP Research Data Repository | oai:figshare.com:article/34057060 | 4 d ago | JSON v1 |
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| concepts[field].anzsrc:group:3101 | mapping · researchdata up ac za | vocabulary-mapper@1.0.0 | keywords['Cell Biology'] |
| concepts[field].anzsrc:group:3104 | mapping · researchdata up ac za | vocabulary-mapper@1.0.0 | keywords['Evolutionary Biology'] |
| concepts[field].anzsrc:group:3104 | mapping · grantsdata jst go jp | vocabulary-mapper@1.0.0 | keywords['Evolutionary Biology'] |
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| concepts[field].local:field:chemistry | mapping · repository lboro ac uk | connector:repository_lboro_ac_uk@1.0.0 | |
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| publication_date | source · repository lboro ac uk | connector:repository_lboro_ac_uk@1.0.0 | |
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