| 基于三氰基铁(Ⅲ)酸盐的FeⅢ4NiⅡ2六核配合物的合成、结构及磁性 |
| Synthesis, crystal structure, and magnetic properties of a cyanide-bridged FeⅢ4NiⅡ2 hexa-nuclear complex based on tricyanideferrate(Ⅲ) |
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| 摘要: 利用三氰基铁酸盐(Bu4N)[FeⅢ(Tp)(CN)3](Tp=氢化三(1-吡唑基)硼酸)与配体2，9-二吡唑基-1，10-菲咯啉(dpzpen)以及高氯酸镍反应合成了一例氰根桥联的FeⅢ4NiⅡ2六核配合物[Fe4Ni2(Tp)4(CN)12(dpzpen)2]·12H2O·3CH3OH(1)。结构研究表明配合物1具有近似菱形的FeⅢ2NiⅡ2骨架结构，另外2个Fe(Ⅲ)则通过氰根延伸在菱形的外侧。磁性研究表明在配合物1中氰根桥联的Fe(Ⅲ)和Ni(Ⅱ)表现出铁磁相互作用。更为重要的是，基于配合物1的结构模型，对它的变温磁化率数据进行拟合得到了不同Fe(Ⅲ)-Ni(Ⅱ)之间的磁耦合常数，得到的最佳磁耦合常数J3d (15.73 cm-1)>J2d (3.53 cm-1)≈J1d (3.50 cm-1)与Ni—N键的键长以及Ni—N≡C键角的变化趋势有关(J3d： 0.206 5 nm，169.8°； J2d： 0.206 2 nm，163.1°； J1d： 0.198 7 nm，161.6°)。以上结果表明Ni—N键长越短，Ni—N≡C键角越大，Fe(Ⅲ)与Ni(Ⅱ)之间的铁磁耦合越强。 |
| 关键词: 三氰基铁酸盐 FeNi配合物 晶体结构 磁性 磁性-结构相互关系 |
| 基金项目: 中央高校基本科研业务费专项资金(No.2023QN1010)资助。 |
| Abstract: A cyanide-bridged FeⅢ4NiⅡ2 hexa-nuclear complex [Fe4Ni2(Tp)4(CN)12(dpzpen)2] ·12H2O·3CH3OH (1) (Tp=hydrotris(pyrazolyl)borate, dpzpen=2,9-di(pyrazo-1-yl)-1,10-phenanthroline) was prepared by the reaction of tricyanideferrate (Ⅲ) (Bu4N) [FeⅢ(Tp)(CN)3] with ligand dpzpen and NiⅡ salt. Structural analysis indicates that two [FeⅢ (Tp) (CN)3]- units bridge two [NiⅡ (dpzpen)]2+ fragments forming an approximately rhombic FeⅢ2NiⅡ2 skeleton with another two [FeⅢ(Tp)(CN)3]- hanging outside the rhombus through cyanide bridges. Magnetic studies show that complex 1 exhibits ferromagnetic interaction between FeⅢ and NiⅡ through cyanide groups. More significantly, the magnetic -structural relationship of complex 1 was established by fitting the temperature dependence of magnetic susceptibility based on its structural model. The best-fitting parameters J3d (15.73 cm-1) > J2d (3.53 cm-1) ≈ J1d (3.50 cm-1) were in good agreement with the variation tendency of corresponding Ni—N bond lengths and Ni—N≡C angles (J3d: 0.206 5 nm, 169.8°; J2d: 0.206 2 nm, 163.1°; J1d: 0.198 7 nm, 161.6°), indicating a shorter Ni—N bond length and a larger Ni—N≡C angle in favor of ferromagnetic interaction for cyanide-bridged FeⅢ-NiⅡ system. |
| Keywords: tricyanideferrate(Ⅲ) FeⅢNiⅡ complex crystal structure magnetic property magnetic-structural relationship |
| 投稿时间：2023-02-23 修订日期：2023-05-08 |
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| 李国玲,王蒙蒙,唐新学,张然,倪中海.基于三氰基铁(Ⅲ)酸盐的FeⅢ4NiⅡ2六核配合物的合成、结构及磁性[J].无机化学学报,2023,39(8):1564-1570. |
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| Support information: 相关附件： 230048_Supporting_Information.pdf |
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