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Axial Ligand as a Critical Factor for High-Performance Pentagonal Bipyramidal Dy(III) Single-Ion Magnets
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-11-23 , DOI: 10.1021/acs.inorgchem.2c02476
Ben Zhang 1 , Xuefeng Guo 2 , Pengfei Tan 1 , Wei Lv 3 , Xiaoye Bai 1 , Yang Zhou 1 , Aihua Yuan 1 , Lei Chen 1 , Dan Liu 2 , Hui-Hui Cui 4 , Ruosong Wang 5 , Xue-Tai Chen 3
Affiliation  

The choice of axial ligands is of great importance for the construction of high-performance Dy-based single-molecule magnets (SMMs). Here, combining axial ligands Ph3SiO (anion of triphenylsilanol) and 2,6-dichloro-4-nitro-PhO (the anion of 2,6-dichloro-4-nitrophenol) with a neutral macrocyclic ligand 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),2,13,15,17-pentaene (L2N5) generates two new pentagonal bipyramidal Dy(III) complexes [DyIII(L2N5) (X)2](BPh4) (X = Ph3SiO, 1; 2,6-dichloro-4-nitro-PhO, 2) with strong axial ligand fields. Magnetic characterizations show that 1 possesses a large energy barrier above 1000 K and a magnetic hysteresis up to 9 K, whereas 2 only displays field-induced peaks of alternating-current susceptibilities without the hysteresis loop, even though 2 has a similar coordination geometry with 1. Detailed Ab initio calculations indicate an apparent difference in the axial negative charge between both complexes, which is caused by the diverse electron-donating properties of the axial ligands. The present work provides an efficient strategy to enhance the SMMs’ properties, which highlights that the electron-donating property of the axial ligands is especially important for constructing the high-performance Dy-based SMMs.

中文翻译:

轴向配体作为高性能五角双锥形 Dy(III) 单离子磁体的关键因素

轴向配体的选择对于构建高性能 Dy 基单分子磁体 (SMM) 非常重要。此处,将轴向配体 Ph 3 SiO (三苯基硅烷醇的阴离子)和 2,6-二氯-4-硝基-PhO (2,6-二氯-4-硝基苯酚的阴离子)与中性大环配体 2,14- 结合dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),2,13,15,17-pentaene (L 2 N5 ) 生成两个新的五角双锥形 Dy(III) 配合物 [ Dy III (L 2 N5 ) (X) 2 ](BPh 4 ) (X = Ph 3 SiO , 1 ; 2,6-二氯-4-硝基-PhO , 2 ) 具有强轴向配体场。磁性表征表明1具有高于 1000 K 的大能垒和高达 9 K 的磁滞,而2仅显示没有磁滞回线的交流磁化率的场感应峰值,即使2具有与1相似的配位几何结构. 详细的从头计算表明两种配合物之间的轴向负电荷存在明显差异,这是由轴向配体的不同供电子特性引起的。目前的工作提供了一种有效的策略来增强 SMM 的性能,突出表明轴向配体的给电子特性对于构建高性能 Dy 基 SMM 尤为重要。
更新日期:2022-11-23
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