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Radical-Bridged Heterometallic Single-Molecule Magnets Incorporating Four Lanthanoceniums. | LitMetric
The syntheses and magnetic properties of organometallic heterometallic compounds [K(THF) ]{Co [(μ -HAN)RE Cp* ] } (1-RE) and [K(Crypt)] {Co [(μ -HAN)RE Cp* ] } (2-RE) containing hexaazatrinaphthylene radicals (HAN⋅ ) and four rare earth (RE) ions are reported. 1-RE shows isolable species with ligand-based mixed valency as revealed by cyclic voltammetry (CV) thus leading to the isolation of 2-RE via one-electron chemical reduction. Strong electronic communication in mixed-valency supports stronger overall ferromagnetic behaviors in 2-RE than 1-RE containing Gd and Dy ions. Ac magnetic susceptibility data reveal 1-Dy and 2-Dy both exhibit slow magnetic relaxation. Importantly, larger coercive field was observed in the hysteresis of 2-Dy at 2.0 K, indicating the enhanced SMM behavior compared with 1-Dy. Ligand-based mixed-valency strategy has been used for the first time to improve the magnetic coupling in lanthanide (Ln) SMMs, thus opening up new ways to construct strongly coupled Ln-SMMs.
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