基于三氰基铁 (Ⅲ )酸盐的 Fe4Ni六核配合物的合成、结构及磁性

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

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

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Author(s)

Detail(s)

Original languageChinese (Simplified)
Pages (from-to)1564-1570
Journal / PublicationChinese Journal of Inorganic Chemistry
Volume39
Issue number8
Publication statusPublished - Aug 2023

Abstract

利用三氰基铁酸盐 (Bu4N) [Fe(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Fe4Ni六核配合物 [Fe4Ni(Tp)(CN)12 (dpzpen)2]·12H2O·3CH3OH (1)。结构研究表明配合物1具有近似菱形的Fe2Ni2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。
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 tri‑ cyanideferrate (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. © 2023 Chinese Chemical Society. All rights reserved.

Research Area(s)

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

Citation Format(s)

基于三氰基铁 (Ⅲ )酸盐的 Fe4Ni六核配合物的合成、结构及磁性. / 李国玲; 王蒙蒙; 唐新学 et al.
In: Chinese Journal of Inorganic Chemistry, Vol. 39, No. 8, 08.2023, p. 1564-1570.

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review