Citation: ZHANG Ke, WANG Hui-Sheng, YU Ling-Yan, CHEN Yong, PAN Zhi-Quan. Research Progress and Prospect on the First Series Transition Metal-Dy Single Molecule Magnets[J]. Chinese Journal of Inorganic Chemistry, ;2020, 36(12): 2205-2226. doi: 10.11862/CJIC.2020.264 shu

Research Progress and Prospect on the First Series Transition Metal-Dy Single Molecule Magnets

School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430205, China

Corresponding author: WANG Hui-Sheng, wangch198201@163.com
Received Date: 28 June 2020
Revised Date: 2 October 2020

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Among the first series transition metal (TM) ions, not only the paramagnetic TM ions (such as Cr^Ⅲ, Mn^Ⅱ/ Mn^Ⅲ, Fe^Ⅱ/Fe^Ⅲ, Co^Ⅱ, Ni^Ⅱ and Cu^Ⅱ) but also diamagnetic TM ions (such as Co^Ⅲ and Zn^Ⅱ) can assemble with Dy^Ⅲ to form the TM-Dy single molecule magnets (TM-Dy SMMs). In this paper, we survey most of the TM-Dy complexes with SMM behavior. For the TM-Dy SMMs, two interesting phenomena should be emphasized on. One is some Cr-Dy complexes possessing relatively high blocking temperature (T_B) and large coercivities, which could be ascribed to the strong magnetic couplings between Cr^Ⅲ and Dy^Ⅲ ions (|J|>10 cm^-1). Another is the Fe^Ⅱ₂-Dy complex with the energy barrier of 319 cm^-1 (459 K), which is high among the TM-Dy SMMs. The reason might be that the axial symmetry of the coordination of Dy^Ⅲ ion is high (D_5h). Additionally, ab initio calculations indicate the excited state also possess high axial symmetry. Besides the Cr^Ⅲ-Dy and Fe^Ⅱ₂-Dy complexes, other TM-Dy SMMs usually exhibits relatively low energy barriers, which may be due to the weak magnetic interactions between paramagnetic TM ions and Dy^Ⅲ ions. To elimate the effect of the weak magnetic couplings on the relaxation behavior, the study of the DTM-Dy SMMs (DTM=diamagnetic the first series transition metal ions such as Co^Ⅲ and Zn^Ⅱ) has been received wide attention and their number is dramatically increasing. For the Zn-Dy SMMs, the number of the Zn₂Dy trinuclear complexes is larger than that of other Zn-Dy complexes, indicating that the Zn₂Dy received more attention. The reason might be that the coordination geometry of the Dy^Ⅲ in the Zn₂Dy complexes can be more easily modulated. Finally, we provided some reseach thoughts for further improving the SMM performance of the TM-Dy complexes; the most important thoughts are that the axial symmetry of the coordination geometries of Dy^Ⅲ ions and the distribution of charge density of Dy^Ⅲ ions in TM-Dy complexes should be controlled. For Dy^Ⅲ in the TM-Dy complexes, the electrostatic repulsion between the Dy^Ⅲ ground-m_J charge density and the ligand charge density should be minimized.
- single molecule magnets,
- the first series transition metal-Dy single molecule magnets,
- coordination geometries,
- easy magnetization axes,
- magnetic couplings
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