Fine-Tuning Ligand to Modulate the Magnetic Anisotropy in a Carboxylate-Bridged Dy2 Single-Molecule Magnet System
2016
A series of dinuclear Dy(III) compounds with the general formula [Dy2(μ2-anthc)4(anthc)2(L)2] (anthc– = 9-anthracenecarboxylate, L = 2,2′-bipyridyl (1), 1,10-phenanthroline (2), and 4,7-dimethyl-1,10-phenanthroline (3)) were synthesized and magnetically characterized. These compounds exhibit single-molecule magnet (SMM) behavior in the absence of the direct-current field, which is rarely observed for carboxylate-bridged dinuclear Dy2 system. With the first coordination sphere of Dy(III) centers being fixed, the energy barrier was modulated by sequentially modifying the terminal neutral L ligands in this Dy2 system. Theoretical calculations revealed that the symmetry of the charge distribution surrounding the Dy(III) centers in 1–3 is the decisive factor to determine the relaxation of the SMMs. The combination of the larger charge distribution along the magnetic axis and lower charge distribution in the equatorial plane (hard plane) formed by five coplanar coordination atoms including two N atoms provided ...
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