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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
Adam T. Hand (14149152)
Alexandria N. Bone (13168780)
Shashank V. Rao (25302724)
Brandon D. Watson-Sanders (25302727)
Adiat A. Fakolujo (23714879)
Yongqiang Cheng (1428478)
Mykhaylo Ozerov (5810771)
J. Krzystek (1415551)
Zheng Gai (1668583)
Wei Lv (319498)
Xue-Tai Chen (1755898)
You Song (587198)
Luke L. Daemen (1818202)
Xiaoping Wang (110673)
Mihail Atanasov (1325127)
Frank Neese (736441)
Zi-Ling Xue (1414108)
Biophysics
Physical Sciences not elsewhere classified
Cell Biology
Physiology
Pharmacology
Biotechnology
Evolutionary Biology
Chemical Sciences not elsewhere classified
Inorganic Chemistry
inelastic neutron scattering
firms using results
crystallographic unit cells
calculations also indicate
firms ), high
distorted octahedral complexes
): ligand field
2 –</ sup
dft phonon calculations
ab initio </
>< sub ><
probing magnetic anisotropy
sup >–</ sup
iv </ sup
</ b >.
</ b >,
calculations reveal
magnetic anisotropy
phonon couplings
hfepr ),
coordinate complexes
shows field
magnetic anisotropies
field splitting
field epr
≥ 1
three different
sole source
smm performance
overlapping orbitals
one unique
molecule magnet
ir magneto
ins )].
induced smm
increased covalency
h </
atom effect
advanced spectroscopies
ac susceptibility
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. 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>. 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.
2026-10-02T00:00:00Z
Dataset
Dataset
10.1021/acs.inorgchem.6c04158.s001
https://figshare.com/articles/dataset/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/34057060
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