Citation: Min LI, Hai-Peng WU, Sheng ZHANG, Yu-Fang LIU, Yong-Qiang CHEN, San-Ping CHEN. Replacement of Carboxylate Ligand Substituent on Modulation of Structures and Magnetic Properties in Salen-Type Dinuclear Dy(Ⅲ) Complexes[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(1): 171-180. doi: 10.11862/CJIC.2022.017 shu

Replacement of Carboxylate Ligand Substituent on Modulation of Structures and Magnetic Properties in Salen-Type Dinuclear Dy(Ⅲ) Complexes

1.
Department of Chemistry and Chemical Engineering, Jinzhong University, Jinzhong, Shanxi 030619, China
2.
College of Chemistry and Materials Science, Northwest University, Xi'an 710127, China
3.
College of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji, Shaanxi 721013, China

Corresponding author: Hai-Peng WU, wuhp@jzxy.edu.cn Yong-Qiang CHEN, chenyongqiang@jzxy.edu.cn San-Ping CHEN, sanpingchen@126.com
Received Date: 8 August 2021
Revised Date: 31 October 2021

Figures(7)

Three salen - type centrosymmetric dinuclear Dy (Ⅲ) complexes, [Dy₂(Hhms)₂(C(CH₃)₃COO)₂(H₂O)₄](NO₃)₂ (1), [Dy₂(Hhms)₂(C₁₄H₉COO)₂(C₂H₅OH)₂(CH₃OH)₂][ZnCl₄] (2), and [Dy₂(Hhms)₂(C₆H₃(NH₂)₂COO)₂Cl₂]·2CH₃CN (3) (H₂hms=(2-hydroxy-3-methoxybenzylidene)-semicarbazide), were isolated with different substituted carboxylic acid ligand, and were characterized structurally and magnetically. Structural analyses illustrate that the Dy (Ⅲ) ions in complexes 1 and 2 maintain similar monocapped square-antiprism geometries, but the coordination mode of carboxylate in 1 is different from that in 2; complexes 2 and 3 possess similar phenoxy oxygen and carboxylate bridged structure whereas the coordination geometries around the Dy(Ⅲ) ions are different between 3 and 2 due to the difference of coordinated small molecules. Magnetic characterizations reveal that significant single - molecule magnet (SMM) behavior was observed under zero dc field for complex 3, with an effective energy barrier to the reversal of magnetization of 96 K. Conversely, complex 1 only showed fast quantum tunneling relaxation even 2 was SMM-silent. Furthermore, the magneto-structural correlations in these Dy₂ complexes were discussed. The results indicate that utility of carboxylate ligand substituent can give rise to good modulation in the molecular anisotropy and symmetry, hence the enhanced magnetic relaxation.
- dinuclear complex,
- dysprosium,
- magnetic properties,
- carboxylate ligand,
- single-molecule magnets
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