Structural Design of Easy-Axis Magnetic Anisotropy and Determination of Anisotropic Parameters of Ln(III)-Cu-II Single-Molecule Magnets

Four dinuclear Le(III)-Cu-II complexes with Ln = Tb (1), Dy (2), Ho (3), and Er (4) were synthesized to investigate the relationship between their respective magnetic anisotropies and ligand-field geometries. These complexes were crystallographically isostructural, and a uni-axial ligand field was achieved by using three phenoxo oxygen groups. Complexes 1 and 2 displayed typical single-molecule magnet (SMM) behaviors, of which the out-of-phase susceptibilities were observed in the temperature range of 1.8-5.0 K (1) and 1.8-20.0 K (2). The Cole-Cole plots exhibited a semicircular shape with alpha parameters in the range of 0.08-0.18 (2.6-4.0 K) and 0.07-0.24 (3.5-7.0 K). The energy barriers Delta/k(B) were estimated from the Arrhenius plots to be 32.9(4) K for 1 and 26.0(5) K for 2. Complex 3 displayed a slow magnetic relaxation below 3.0 K, whereas complex 4 did not show any frequency-dependent behavior for both in-phase and out-of-phase susceptibilities, which indicates that easy-axis anisotropy was absent. The temperature dependence of the dc susceptibilities for the field-aligned samples of 1-3 revealed that the chi T-M value continuously increased as the temperature was lowered, which indicates the presence of low-lying Stark sublevels with the highest vertical bar J(z)vertical bar values. In contrast, complex 4 displayed a smaller and temperature-independent chi T-M value, which also indicates that easy-axis anisotropy was absent. Simultaneous analyses were carried out for 1-3 to determine the magnetic anisotropy parameters on the basis of the Hamiltonian that considers B-2(0), B-4(0), and B-6(0).