Synthesis, crystal structure, and magnetic properties of a cyanide⁃bridged Fe4Ni2 hexa⁃nuclear complex based on tricyanideferrate(Ⅲ)


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Original languageEnglish
Pages (from-to)1564-1570
Journal / PublicationChinese Journal of Inorganic Chemistry
Issue number8
Publication statusPublished - Aug 2023


A cyanide - bridged Fe4Ni2 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) [Fe (Tp) (CN)3] with ligand dpzpen and Ni salt. Structural analysis indicates that two [Fe (Tp) (CN)3] - units bridge two [Ni (dpzpen)]2+ fragments forming an approximately rhombic Fe2Ni2 skeleton with another two [Fe(Tp)(CN)3]- hanging outside the rhombus through cyanide bridges. Magnetic studies show that complex 1 exhibits ferromagnetic interaction between Fe and Ni 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 Fe - Ni system. CCDC: 2239885.
利用三氰基鐵酸鹽(Bu4N)[Fe(Tp)(CN)3](Tp=氫化三(1-吡唑基)硼酸)與配體2,9-二吡唑基-1,10-菲咯啉(dpzpen)以及高氯酸鎳反應合成了一例氰根橋聯的Fe4Ni2六核配合物[Fe4Ni2(Tp)4(CN)12(dpzpen)2]·12H2O·3CH3OH (1)。結構研究表明配合物1具有近似菱形的Fe2Ni2骨架結構,另外2個Fe(Ⅲ)則通過氰根延伸在菱形的外側。磁性研究表明在配合物1中氰根橋聯的Fe(Ⅲ)和Ni(Ⅱ)表現出鐵磁相互作用。更為重要的是,基於配合物1的結構模型,對它的變溫磁化率數據進行擬合得到了不同Fe(Ⅲ)-Ni(Ⅱ)之間的磁耦合常數,得到的最佳磁耦合常數J3d(15.73 cm-1)>J2d(3.53 cm-1)≈J1d(3.50 cm-1)與Ni—N鍵的鍵長以及Ni—N≡C鍵角的變化趨勢有關(J3d:0.206 5 nm,169.8°;J2d:0.206 2 nm,163.1°;J1d:0.198 7 nm,161.6°)。以上結果表明Ni—N鍵長越短,Ni—N≡C鍵角越大,Fe(Ⅲ)與Ni(Ⅱ)之間的鐵磁耦合越強。

Research Area(s)

  • tricyanideferrate(Ⅲ), FeⅢNiⅡ complex, crystal structure, magnetic-structural relationship, magnetic property, 三氰基铁酸盐, FeNi 配合物, 晶体结构, 磁性, 磁性-结构相互关系

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