Molecular Orientation of a Terbium(III)-Phthalocyaninato Double-Decker Complex for Effective Suppression of Quantum Tunneling of the Magnetization.

Single-molecule magnet (SMM) properties of crystals of a terbium(III)-phthalocyaninato double-decker complex with different molecular packings (: TbPc₂, : TbPc₂·CH₂Cl₂) were studied to elucidate the relationship between the molecular packing and SMM properties. From single crystal X-ray analyses, the high symmetry of the coordination environment of suggested that the SMM properties were improved. Furthermore, the shorter intermolecular Tb-Tb distance and relative collinear alignment of the magnetic dipole in indicated that the magnetic dipole-dipole interactions were stronger than those in . This was confirmed by using direct current magnetic measurements. From alternating current magnetic measurements, the activation energy for spin reversal for and were similar. However, the relaxation time for is three orders of magnitude slower than that for in the low- region due to effective suppression of the quantum tunneling of the magnetization. These results suggest that the SMM properties of TbPc₂ highly depend on the molecular packing.