Series of Benzoquinone-Bridged Dicobalt(II) Single-Molecule Magnets

Mononuclear complexes within a particular coordination geometry have been well recognized for high-performance single-molecule magnets (SMMs), while the incorporation of such well-defined geometric ions into multinuclear complexes remains less explored. Using the rigid 2-(di(1H-pyrazol-1-yl)methyl)-6-(1H-pyrazol-1-yl)pyridine (PyPz₃) ligand, here, we prepared a series of benzoquinone-bridged dicobalt(II) SMMs [{(PyPz₃)Co}₂(L)][PF₆]₂, (1, L = 2,5-dioxo-1,4-benzoquinone (dhbq^2-); 2, L = chloranilate (CA^2-); and 3, L = bromanilate (BA^2-)), in which each Co(II) center adopts a distorted trigonal prismatic (TPR) geometry and the distortion increases with the sizes of 3,6-substituent groups (H (1) < Cl (2) < Br (3)). Accordingly, the magnetic study revealed that the axial anisotropy parameter (D) of the Co ions decreased from -78.5 to -56.5 cm^-1 in 1-3, while the rhombic one (E) increased significantly. As a result, 1 exhibited slow relaxation of magnetization under a zero dc field, while both 2 and 3 showed only the field-induced SMM behaviors, likely due to the increased rhombic anisotropy that leads to the serious quantum tunneling of the magnetization. Our study demonstrated that the relaxation dynamics and performances of a multinuclear complex are strongly dependent on the coordination geometry of the local metal ions, which may be engineered by modifying the substituent groups.