Authors
Adam T Hand, Alexandria N Bone, Shashank V Rao, Brandon D Watson-Sanders, Adiat A Fakolujo, Yongqiang Cheng, Mykhaylo Ozerov, J Krzystek, Zheng Gai, Wei Lv, Xue-Tai Chen, You Song, Luke L Daemen, Xiaoping Wang, Mihail Atanasov, Frank Neese, Zi-Ling Xue
Published in
Inorganic chemistry. Volume 65. Issue 41. Pages 24492-24504. Oct 19, 2026.
Abstract
In six-coordinate complexes with S ≥ 1, deviations from perfect Oh geometry lead to magnetic anisotropy. We have studied (NBun4)2[ReIVX6] (Re-X; X = Cl, Br, I; S = 3/2), including zero-field splitting (ZFS) in Re-I, by advanced spectroscopies [far-IR magneto-spectroscopy (FIRMS), high-frequency and -field EPR (HFEPR), and inelastic neutron scattering (INS)]. AC susceptibility of Re-I shows field-induced SMM (single-molecule magnet) properties. Unlike Re-I with one unique [ReI6]2- center, there are four and three different [ReX6]2- centers in the crystallographic unit cells of Re-Cl and Re-Br, respectively. Ab initio calculations determine ZFS parameters and show that magnetic anisotropies are influenced by deviations from the Oh geometry and by increased covalency from Re-Cl to Re-Br to Re-I. Although Re-X bond lengths increase from Re-Cl to Re-Br to Re-I, the calculations reveal that the longer Re-I bonds are compensated by the diffuse, better-overlapping orbitals of I- ligands. The diffuseness in ligand orbitals likely contributes to the SMM performance of Re-I. The calculations also indicate that deviations from the Oh geometry in [ReX6]2- ions are the sole source of magnetic anisotropy and that there is no heavy-atom effect from the halide ligands. Spin-phonon couplings in Re-I have been probed by FIRMS using results from DFT phonon calculations.
PMID:
42895385
Bibliographic data and abstract were imported from PubMed on 19 Oct 2026.
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