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Magneto-structural Correlations in Ni 2+ -Halide···Halide-Ni 2+ Chains.
- Source :
-
Inorganic chemistry [Inorg Chem] 2022 Jan 10; Vol. 61 (1), pp. 141-153. Date of Electronic Publication: 2021 Dec 23. - Publication Year :
- 2022
-
Abstract
- We present the magnetic properties of a new family of S = 1 molecule-based magnets, NiF <subscript>2</subscript> (3,5-lut) <subscript>4</subscript> ·2H <subscript>2</subscript> O and NiX <subscript>2</subscript> (3,5-lut) <subscript>4</subscript> , where X = HF <subscript>2</subscript> , Cl, Br, or I (lut = lutidine C <subscript>7</subscript> H <subscript>9</subscript> N). Upon creation of isolated Ni-X···X-Ni and Ni-F-H-F···F-H-F-Ni chains separated by bulky and nonbridging lutidine ligands, the effect that halogen substitution has on the magnetic properties of transition-metal-ion complexes can be investigated directly and in isolation from competing processes such as Jahn-Teller distortions. We find that substitution of the larger halide ions turns on increasingly strong antiferromagnetic interactions between adjacent Ni <superscript>2+</superscript> ions via a novel through-space two-halide exchange. In this process, the X···X bond lengths in the Br and I materials are more than double the van der Waals radius of X yet can still mediate significant magnetic interactions. We also find that a simple model based on elongation/compression of the Ni <superscript>2+</superscript> octahedra cannot explain the observed single-ion anisotropy in mixed-ligand compounds. We offer an alternative that takes into account the difference in the electronegativity of axial and equatorial ligands.
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 61
- Issue :
- 1
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 34939800
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.1c02483