The rotation of the coordinating plane of the square-antiprismatic environment induces a magnetic relaxation path through higher excited states, offering a new way to modulate the geometries of lanthanides to facilitate magnetic relaxation climbing up to higher energy levels.
A unique Dy6 complex with a planar Dy3 + Dy3 structure was assembled by delicately modifying the axial ligands. Single-molecule magnet behavior and meanwhile a toroidal magnetic moment in the ground state have been observed.
Reactions of Ln(III) perchlorate (Ln = Gd, Tb, Dy, and Ho), NiCl2·6H2O, and a polydentate Schiff base resulted in the assembly of novel isostructural hexanuclear Ni4Ln2 complexes [Ln = Gd (1), Tb (2), Dy (3), Ho (4)] with an unprecedented 3d-4f metal topology consisting of two defect-dicubane units. The corresponding Ni4Y2 (5) complex containing diamagnetic Y(III) atoms was also isolated to assist the magnetic studies. Interestingly, complexes 2 and 3 exhibit SMM characteristics and 4 shows slow relaxation of the magnetization. The absence of frequency-dependent in-phase and out-of-phase signals for the Ni-Y species suggests that the Ln ions' contribution to the slow relaxation must be effectual as previously observed in other Ni-Dy samples. However, the observation of χ″ signals with zero dc field for the Ni-Tb and Ni-Ho derivatives is notable. Indeed, this is the first time that such a behavior is observed in the Ni-Tb and Ni-Ho complexes.
Toroidal arrangements of magnetic moments are realized in heterometallic LnCu (Ln = Tb and Dy) macrocycles thanks to the magnetic coupling between lanthanide and 3d metal ions.
A series of mononuclear Dy complexes with the general formula [DyLz(salicylaldehyde)]·X·solvent (Lz = 6-pyridin-2-yl[1,3,5]triazine-2,4-diamine; X = OH (1·OH), Cl (2·Cl), Br (3·Br)) have been synthesized using mixed salicylaldehyde/pyridinyl-triazine ligands and discriminative counteranions. The Dy ion in these three complexes resides in a similar D coordination geometry with counteranions perturbing the coordination environment and bond lengths and angles in the lattice. Magnetostructural studies reveal that the asymmetric distribution of salicylaldehyde/pyridinyl-triazine ligands and the presence of discriminative counteranions result in the coexistence of large anisotropy and quantum tunneling of magnetization. The magnetic anisotropy is dominated by the axial ligand field with short Dy-O distances and large ∠O-Dy-O angles, while the quantum tunneling relaxation is probably dictated by the π-π stacking of the Lz ligands, which induces an axial constriction of the coordinating plane. Ab initio calculations substantiate the diversity of the magnetic behaviors in these complexes and highlight the importance of axial ligand field with short Dy-O distances, large ∠O-Dy-O angles and less ligand stacking in these pseudo-D-symmetrical single-molecule magnets.
The self-assembly of three giant hexagonal 3d-4f metallocycles with inner diameters of 16.4, 16.5, and 16.4 Å, is described. Hexagonal metallocycles were stacked along the crystallographic c axis, producing unique hexagonal macroscopic tubular single crystals. The assembly mechanism of the tubular crystals was investigated. Remarkably, all three hexagonal metallocycles show typical single-molecule magnet behavior, benefiting from the ferromagnetic couplings between the 3d and 4f ions.
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