Multiple-decker phthalocyaninato dinuclear lanthanoid(iii) single-molecule magnets with dual-magnetic relaxation processes

The SMM behaviour of dinuclear Ln(iii)-Pc multiple-decker complexes (Ln = Tb³⁺ and Dy³⁺) with energy barriers and slow-relaxation behaviour were explained by using X-ray crystallography and static and dynamic susceptibility measurements. In particular, interactions among the 4f electrons of several dinuclear Ln(iii)-Pc type SMMs have never been discussed on the basis of the crystal structure. For dinuclear Tb(iii)-Pc complexes, a dual magnetic relaxation process was observed. The relaxation processes are due to the anisotropic centres. Our results clearly show that the two Tb³⁺ ion sites are equivalent and are consistent with the crystal structure. On the other hand, the mononuclear Tb(iii)-Pc complex exhibited only a single magnetic relaxation process. This is clear evidence that the magnetic relaxation mechanism depends heavily on the dipole-dipole (f-f) interactions between the Tb³⁺ ions in the dinuclear systems. Furthermore, the SMM behaviour of dinuclear Dy(iii)-Pc type SMMs with smaller energy barriers compared with that of Tb(iii)-Pc and slow-relaxation behaviour was explained. Dinuclear Dy(iii)-Pc SMMs exhibited single-component magnetic relaxation behaviour. The results indicate that the magnetic relaxation properties of dinuclear Ln(iii)-Pc multiple-decker complexes are affected by the local molecular symmetry and are extremely sensitive to tiny distortions in the coordination geometry. In other words, the spatial arrangement of the Ln³⁺ ions (f-f interactions) in the crystal is important. Our work shows that the SMM properties can be fine-tuned by introducing weak intermolecular magnetic interactions in a controlled SMM spatial arrangement.