二价金属镍磁性配合物的合成、单晶结构及磁性研究

摘要/Abstract

摘要： 本文以5-((4-羧基苯氧基)-甲基)间苯二甲酸(H₃L)为含氧主配体,通过含N辅配体1,4-二(1H-咪唑-1-基)苯(1,4-bib)的配位,与Ni(II)离子在水热条件下反应合成了一例具有三维框架结构的配合物[Ni₃(L^3-)₂(1,4-bib)₄(H₂O)₂]·5H₂O (1)。通过单晶X射线衍射、粉末X射线衍射和元素分析对配合物1的结构进行了表征。配合物1结晶于三斜晶系P-1空间群,其晶体学参数:a=1.260 5(7) nm,b=1.349 1(7) nm,c=1.364 8(7) nm,α=111.913(8)°,β=117.251(7)°,γ=90.732(8)°,V=1.866 2(18) nm³,Z=1,M_r=1 769.66,F(000)=916,μ=0.84 mm^-1,D_c=1.575 mg·m^-3,S=1.06,R₁=0.056,wR₂=0.159。半刚性三羧酸配体L^3-和刚性1,4-bib的共同贡献构筑了可预测的高维结构,Ni离子通过N、O原子的配位及配体的结构延伸促使配合物1形成三维网络。此外,研究了含单d电子中心Ni(II)配合物的磁性能:配合物1中羧基仅与一个阳离子结合,导致固体中的磁性由金属单离子行为决定。配合物1的变温磁化率χ_mT可以通过零场分裂来描述。

关键词: Ni(II)离子, 配合物, 晶体结构, 三维框架结构, 磁性

Abstract: The synthesis of a novel complex [Ni₃(L^3-)₂(1,4-bib)₄(H₂O)₂]·5H₂O (1) with three-dimensional framework structure was achieved through a hydrothermal reaction, employing 5-((4-carboxylphenoxy)-methyl) isophthalic acid (H₃L) as the main oxygen-containing ligand, complemented by the N-donor ligand 1,4-bis(1H-imidazol-1-yl)benzene (1,4-bib), and Ni(II) ions. The structure of complex 1 was characterized by single crystal X-ray diffraction, powder X-ray diffraction, and elemental analysis. Complex 1 is crystallized in the triclinic crystal system of P-1 space group, and its crystallographic parameters are a=1.260 5(7) nm, b=1.349 1(7) nm, c=1.364 8(7) nm, α=111.913(8)°, β=117.251(7)°, γ=90.732(8)°, V=1.866 2(18) nm³, Z=1, M_r=1 769.66, F(000)=916, μ=0.84 mm^-1, D_c=1.575 mg·m^-3, S=1.06, R₁=0.056, wR₂=0.159. The joint contribution of semi-rigid tricarboxylic acid ligand L^3-, rigid 1,4-bib and also with Ni(II) ion to form a predictable high-dimensional structure. Complex 1 is a three-dimensional network constructed through the coordination of N and O atoms with Ni ion and the structural extension of the ligand. In addition, the magnetic properties of Ni(II) compound containing single d electron center were studied: the carboxyl group in mononuclear complex 1 only binds to one cation, resulting in magnetism in the solid being determined by the behavior of single metal ions. Variable temperature magnetic susceptibility of χ_mT in complex 1 can be described by zero field splitting.

Key words: Ni(II) ion, complex, crystal structure, three-dimensional framework structure, magnetism

中图分类号:

O641.4

安燕燕, 郭婷婷, 边建红, 赵丹, 闫娟枝. 二价金属镍磁性配合物的合成、单晶结构及磁性研究[J]. 人工晶体学报, 2024, 53(10): 1784-1790.

AN Yanyan, GUO Tingting, BIAN Jianhong, ZHAO Dan, YAN Juanzhi. Synthesis, Single Crystal Structure, and Magnetic Study of Divalent Metal Nickel Magnetic Complex[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(10): 1784-1790.

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