Two {Zn II2DyIII} complexes supported by monophenoxido/dicarboxylate bridges with multiple relaxation processes: carboxylato ancillary ligand-controlled magnetic anisotropy in square antiprismatic DyIII species

Abstract

Two linear-shaped heterometallic trinuclear {Zn^II₂Dy^III} clusters were prepared with a compartmental Schiff-base ligand and carboxylate as the co-ligand. The central Dy^III ion is sandwiched by two [ZnHhms(RCOO)₂] (H₂hms = (2-hydroxy-3-methoxybenzylidene)-semicarbazide) units to form a distorted square antiprismatic (SAP) geometry with D_4d symmetry. The Dy^III and Zn^II ions are triply bridged by one unique monophenoxido/dicarboxylate group, where one of the carboxylates shows a severe angular distortion. The magnetic analysis revealed a field-dependent change with two relaxation processes in 1 and 2, which originated from the molecular magnetic center and dipolar–dipolar coupling. The dipole-induced slow relaxation disappeared upon magnetic-site dilution, while another faster relaxation appeared in the high frequency region associated with the different distortions of the antiprismatic sites for 1 and disordered structures for 2. Ab initio calculations revealed that two {Zn^II₂Dy^III}-carboxylate complexes are axial in nature, but the remarkable quantum tunnelling of the magnetization exists in the ground state, which lowers the anisotropic barrier and prohibits zero-field single-molecule magnet behavior. The crystal field of the carboxylato ancillary ligands produces a competitive effect with the phenoxido bridging ligands on the magnetic anisotropy of the lanthanide ions, which greatly affects the electrostatic distribution of this type of {Zn^II₂Dy^III} single-ion magnets (SIMs). The results offer a model for further investigating structural factors in the relaxation mechanism of SIM systems.