Elucidation of Dual Magnetic Relaxation Processes in Dinuclear Dysprosium(III) Phthalocyaninato Triple-Decker Single-Molecule Magnets Depending on the Octacoordination Geometry

When applying single-molecule magnets (SMMs) to spintronic devices, control of the quantum tunneling of the magnetization (QTM) as well as a spin-lattice interactions are important. Attempts have been made to use not only coordination geometry but also magnetic interactions between SMMs as an exchange bias. In this manuscript, dinuclear dysprosium(III) (Dy^III) SMMs with the same octacoordination geometry undergo dual magnetic relaxation processes at low temperature. In the dinuclear Dy^III phthalocyaninato (Pc²⁻) triple-decker type complex [(Pc)Dy(ooPc)Dy(Pc)] (1) (ooPc²⁻=2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato) with a square-antiprismatic (SAP) geometry, the ground state is divided by the Zeeman effect, and level intersection occurs when a magnetic field is applied. Due to the ground state properties of 1, since the Zeeman diagram where the levels intersect in an H_dc of 2500 Oe, two kinds of QTM and direct processes occur. However, dinuclear Dy^III-Pc systems with C₄ geometry, which have a twist angle (ϕ) of less than 45° do not undergo dual magnetic relaxation processes. From magnetic field and temperature dependences, the dual magnetic relaxation processes were clarified.