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

Yao, Binling1; Zhang, Yi-Quan2; Deng, Yi-Fei1; Li, Tianran1; Zhang, Yuan-Zhu1

2022-09-01

10.1021/acs.inorgchem.2c01851

INORGANIC CHEMISTRY   Impact Factor & Quartile

0020-1669

1520-510X

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 (PyPz(3)) ligand, here, we prepared a series of benzoquinone-bridged dicobalt(II) SMMs [{(PyPz(3))Co}(2)(L)][PF6](2), (1, L = 2,5-dioxo-1,4-benzoquinone (dhbq2-); 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.

SCI

English

NI Journal Papers

First ; Corresponding

Stable Support Plan Program of Shenzhen Natural Science Fund[20200925151834005] ; National Natural Science Founda-tion of China["21901108","22173043"] ; Guangdong Basic and Applied Basic Research Foundation[2022A1515011818]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000862796300001

AMER CHEMICAL SOC

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol SUSTech, Dept Chem, Shenzhen 518055, Peoples R China
2.Nanjing Normal Univ, Sch Phys Sci & Technol, Jiangsu Key Lab NSLSCS, Nanjing 210023, Peoples R China

Yao, Binling,Zhang, Yi-Quan,Deng, Yi-Fei,et al. Series of Benzoquinone-Bridged Dicobalt(II) Single-Molecule Magnets[J]. INORGANIC CHEMISTRY,2022.

Yao, Binling,Zhang, Yi-Quan,Deng, Yi-Fei,Li, Tianran,&Zhang, Yuan-Zhu.(2022).Series of Benzoquinone-Bridged Dicobalt(II) Single-Molecule Magnets.INORGANIC CHEMISTRY.

Yao, Binling,et al."Series of Benzoquinone-Bridged Dicobalt(II) Single-Molecule Magnets".INORGANIC CHEMISTRY (2022).