Abstract
Di-nuclear citrate complexes, [CH6 N3 ]2 [M2 (citH)2 (H2 O)4 ] ⋅ 2H2 O (citH4 =citric acid; M=FeII (Fe-2), CoII (Co-2), and NiII (Ni-2)), are synthesized. The ligand, citH3- , is deprotonated only at the three carboxy groups, which is different from the previously reported tetra-nuclear structures with cit4- ligands. Magnetic measurements reveal that these complexes have intramolecular ferromagnetism with J=∼0 cm-1 (Ni-2), 0.02 cm-1 (Co-2), and 0.04 cm-1 (Fe-2). Co-2 and Fe-2 show slow magnetic relaxation, and are field-induced SMMs with activation energy of spin-reversal Ueff =27 cm-1 (Co-2) and 4.2 cm-1 (Fe-2). Density functional theory calculations indicate that the uniaxial anisotropy along the z-axis of each metal ion center forms the pseudo-serial arrangement, leading to intramolecular ferromagnetism via the magnetic dipole interaction. This work demonstrates the creation of ferromagnetic SMMs by the magnetic dipole engineering of 3d di-nuclear metal ion centers.
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