Two-coordinate transition metal complexes are exciting candidates for single-molecule magnets (SMMs) because their highly axial coordination environments lead to sizeable magnetic anisotropy. We report a series of five structurally related two-coordinate Fe(II) -terphenyl complexes (4-R-2,6-XylCH)Fe [R = Bu (1), SiMe (2), H (3), Cl (4), CF (5)] where, by changing the functionalisation of the -substituent (R), we alter their magnetic function. All five complexes are field-induced single-molecule magnets, with relaxation rates that are well-described by a combination of direct and Raman mechanisms. By using more electron donating R groups we were able to slow the rate of magnetic relaxation. Our calculations predict a large crystal field splitting (>850 cm) and sizeable zero-field splitting parameters ( -60 cm, || < 0.2 cm) for 1-5. These favourable magnetic properties suggest that -terphenyl ligands have untapped potential as chemically versatile ligands able to impose highly axial crystal fields.
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http://dx.doi.org/10.1039/d2dt03531f | DOI Listing |
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