Citation: Tian Haiquan, Zheng Li-Min. Cyclic Lanthanide-based Molecular Clusters: Assembly and Single Molecule Magnet Behavior[J]. Acta Chimica Sinica, ;2020, 78(1): 34-55. doi: 10.6023/A19090330 shu

Cyclic Lanthanide-based Molecular Clusters: Assembly and Single Molecule Magnet Behavior

Tian Haiquan ^a,b ,
Zheng Li-Min ^a,,

a.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023
b.
Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059

Corresponding author: Zheng Li-Min, lmzheng@nju.edu.cn
Received Date: 6 September 2019
Available Online: 6 January 2019
Fund Project: the National Key R & D Program of China 2018YFA0306004the National Natural Science Foundation of China 21731003Project supported by the National Key R&D Program of China (Nos. 2017YFA0303203, 2018YFA0306004) and the National Natural Science Foundation of China (No. 21731003)the National Key R & D Program of China 2017YFA0303203

Figures(34)

Lanthanide-based single molecule magnets have received tremendous attentions in recent years owing to the strong magnetic anisotropies of the lanthanide ions arising from the strong spin-orbital couplings. Cyclic metal clusters, also called molecular wheels or metallacrown ether, are a subclass of metal clusters. From the magnetic point of view, cyclic transition metal clusters can be devided into three types, e.g. ferromagnetically coupled cyclic clusters which favor single molecule magnet behavior, and antiferromagnetically coupled even-or odd-numbered cyclic clusters with S=0 or S=1/2 ground state. The magnetic properties of lanthanide-based cyclic clusters are more complicated because the magnetic interactions between the lanthanide ions are extremely weak. The overall magnetic behavior is largely dominated by the single ion anisotropy and the dipole-dipole interactions between the metal ions. When the anisotropy axes of the lanthanide ions in the cyclic clusters are arranged in a toroidal manner, single-molecule toroics could be achieved. Therefore, the design and synthesis of cyclic lanthanide-based clusters can provide not only new materials with architectural beauty and single molecule magnet behavior, but also single-molecule toroics with vortex distribution of the magnetic dipoles of lanthanide ions, which would have potential applications in information storage, quantum computing, spintronic devices and multiferroic materials. Noting that lanthanide-based single-molecule toroics have been described detailly in several reviews, this article will summarize the current status of the cyclic lanthanide clusters with the focus on the design and assembly strategies, the structural characteristics and magnetic studies. Most work have been concentrated on the Ln₃, Ln₄ and Ln₆ cyclic clusters, including those containing oxygen centers. Examples of even-numbered cyclic clusters Ln_x (x ≥ 8) are much less, and those of odd-numbered cyclic clusters Ln_x (x ≥ 5) are rare. As the cyclic clusters are frequently distorted to different extent, many of them exhibit single molecule magnet behavior, and only few of them show toroic magnetization. It remains future challenges to design and synthesize new lanthanide-based cyclic clusters with regular and flat geometries and toroically arranged magnetic moments, and to achieve the multifunctions in the same molecular composite.
- single molecule magnet,
- lanthanide,
- cyclic cluster,
- self-assembly
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