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Citation: Guo-Ling LI, Meng-Meng WANG, Xin-Xue TANG, Ran ZHANG, Zhong-Hai NI. Synthesis, crystal structure, and magnetic properties of a cyanide-bridged Fe4ⅢNi2Ⅱ hexa-nuclear complex based on tricyanideferrate(Ⅲ)[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(8): 1564-1570. doi: 10.11862/CJIC.2023.119 shu

Synthesis, crystal structure, and magnetic properties of a cyanide-bridged Fe4ⅢNi2Ⅱ hexa-nuclear complex based on tricyanideferrate(Ⅲ)

  • 1.

    School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou, Jiangsu 221116, China

  • 2.

    Department of Materials Science and Engineering, City University of Hong Kong, Hong Kong 999077, China

Figures(4)

  • A cyanide-bridged Fe4ⅢNi2Ⅱ 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 Fe2ⅢNi2Ⅱ 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.
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