| 基于席夫碱分隔配体的Cu-Tb单分子磁体的阴离子调控 |
| Anionic Modification of the Cu-Tb Single-Molecule Magnets Based on the Compartmental Schiff-Base Ligand |
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| 摘要: 基于席夫碱分隔配体H2vanophen（1，2-苯二胺缩邻香草醛），通过引入不同的阴离子，构筑了3个Cu-Tb基金属配合物[Cu2（vanophen）2TbCl2（MeOH）2]Cl·3MeOH（1）、[Cu2（vanophen）2TbCl2（MeOH）2]（TCNQ）1.5·2MeOH（2）和[Cu2（vanophen）2Tb2（N3）6]·2MeOH（3）（TCNQ=7，7，8，8-四氰基对苯二醌二甲烷），并详细研究了它们的结构和磁性。除了抗衡阴离子外，配合物1和2具有非常相似的[CuTbCu]三核结构；其中Cu（Ⅱ）离子处于席夫碱配体中的[N2O2]配位口袋中，而Tb（Ⅲ）离子则和配体中的[O4]配位口袋中的全部或部分O原子配位。对应于一个三核基元，配合物1中的抗衡阴离子为一个Cl-离子，而配合物2中的抗衡阴离子是一个TCNQ-0.5阴离子及半个TCNQ-阴离子。配合物3是由end-end及end-on叠氮桥联2个[CuTb]单元形成的四核[CuTb]2配合物。磁性研究表明，三核配合物1和2均为场致的单分子磁体而配合物3为零场单分子磁体，其中配合物1和3的能垒分别为（11.1±0.3） cm-1和（20.2±0.3） cm-1。相比于配合物1，配合物2具有更低的能垒，这可能源于其中的阴离子自由基和三核[CuTbCu]基元之间的弱的磁相互作用。 |
| 关键词: 单分子磁体 席夫碱分隔配体 阴离子调控 3d-4f配合物 |
| 基金项目: 国家重点研发计划项目（No.2018YFA0306002）和国家自然科学基金（No.21973039）资助 |
| Abstract: 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. |
| Keywords: single-molecule magnet compartmental Schiff-base ligand anionic modification 3d-4f complexes |
| 投稿时间：2022-04-13 修订日期：2022-05-02 |
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| 嵇文杰,夏成才,张新宇,王新益.基于席夫碱分隔配体的Cu-Tb单分子磁体的阴离子调控[J].无机化学学报,2022,38(6):1199-1208. |
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| Support information: 相关附件： 220178_Cu-Tb-220178-SI返修.pdf |
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