Scatena, R; Manson, ZE; Villa, DY; Manson, JL; Allan, DR; Goddard, PA; Johnson, RD; (2025) Electron-density analysis of halide⋯halide through-space magnetic exchange. Journal of Applied Crystallography , 58 pp. 363-373. 10.1107/S1600576725000536.

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Abstract

We present a combined experimental and density functional theory study that characterizes the charge and spin density in NiX2(3,5-lutidine)4 (X = Cl, Br and I). In this material, magnetic exchange interactions occur via Ni2+-halide⋯halide-Ni2+ pathways, forming one-dimensional chains. We find evidence for weak halide⋯halide covalency in the iodine system, which is greatly reduced when X = Br and is absent for X = Cl; this is consistent with the reported 'switching-on' of magnetic exchange in the larger-halide cases. Our results are benchmarked against density functional theory calculations on [NiHF2(pyrazine)2]SbF6, in which the primary magnetic exchange is mediated by F-H-F bridging ligands. This comparison indicates that, despite the largely depleted charge density found at the centre of halide⋯halide bonds, these through-space interactions can support strong magnetic exchange gated by weak covalency and enhanced by significant electron density overlapping that of the transition metal centres.

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