Citation: Wen-Jie JI, Cheng-Cai XIA, Xin-Yu ZHANG, Xin-Yi WANG. Anionic Modification of the Cu-Tb Single-Molecule Magnets Based on the Compartmental Schiff-Base Ligand[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(6): 1199-1208. doi: 10.11862/CJIC.2022.117 shu

Anionic Modification of the Cu-Tb Single-Molecule Magnets Based on the Compartmental Schiff-Base Ligand

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

Corresponding author: Xin-Yi WANG, wangxy66@nju.edu.cn
Received Date: 13 April 2022
Revised Date: 2 May 2022

Figures(7)

By using different anions, three Cu-Tb metal complexes, namely [Cu₂(vanophen)₂TbCl₂(MeOH)₂]Cl· 3MeOH (1), [Cu₂(vanophen)₂TbCl₂(MeOH)₂](TCNQ)_1.5·2MeOH (2), and [Cu₂(vanophen)₂Tb₂(N₃)₆]·2MeOH (3), based on the compartmental Schiff-base ligand H₂vanophen (H₂vanophen=N, N′-bis(2-oxy-3-methoxybenzylidene)-1, 2-phenylenediamine, TCNQ=7, 7, 8, 8-tetracyanoquinodimethane) have been synthesized and characterized structurally and magnetically. Except for the different charge-balancing anions, complexes 1 and 2 have a very similar trinuclear [CuTbCu] structure, where the Cu(Ⅱ) ions are in the [N₂O₄] coordination pockets of the ligands, while the Tb(Ⅲ) ion is coordinated by all or some of the oxygen atoms from the [O₄] pocket of the ligands. The charge-balancing anion is a Cl^- ion in 1, while the positive charge is balanced by one TCNQ^-0.5 radical and a half of the TCNQ^- radical in 2. As for complex 3, it has a tetranuclear [CuTb]₂ structure, where two [CuTb] units are bridged by end-end and end-on azides. Magnetic studies revealed that both 1 and 2 are field-induced SMMs while 3 is a zero-field SMM. The energy barriers of 1 and 3 were estimated to be (11.1±0.3) cm^-1 and (20.2±0.3) cm^-1, respectively. As for complex 2, its energy barrier was lower than that of 1, which might be due to the weak magnetic interaction between the [CuTbCu] unit and the paramagnetic radical anions.
- single-molecule magnet,
- compartmental Schiff-base ligand,
- anionic modification,
- 3d-4f complexes
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