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Magneto-structural Correlations in Ni 2+ -Halide···Halide-Ni 2+ Chains.

Authors :
Blackmore WJA
Curley SPM
Williams RC
Vaidya S
Singleton J
Birnbaum S
Ozarowski A
Schlueter JA
Chen YS
Gillon B
Goukassov A
Kibalin I
Villa DY
Villa JA
Manson JL
Goddard PA
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