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二价金属镍磁性配合物的合成、单晶结构及磁性研究

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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(L3-)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=1.2605(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,Mr=1 769.66,F(000)=916,µ=0.84 mm-1,Dc=1.575 mg·m-3,S=1.06,R1=0.056,wR2=0.159.半刚性三羧酸配体L3-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xmT可以通过零场分裂来描述.
Synthesis,Single Crystal Structure,and Magnetic Study of Divalent Metal Nickel Magnetic Complex
The synthesis of a novel complex[Ni3(L3-)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,Mr=1 769.66,F(000)=916,μ=0.84 mm-1,Dc=1.575 mg·m-3,S=1.06,R1=0.056,wR2=0.159.The joint contribution of semi-rigid tricarboxylic acid ligand L3-,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 xmT in complex 1 can be described by zero field splitting.

Ni(Ⅱ)ioncomplexcrystal structurethree-dimensional framework structuremagnetism

安燕燕、郭婷婷、边建红、赵丹、闫娟枝

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太原学院材料与化学工程系,太原 030032

Ni(Ⅱ)离子 配合物 晶体结构 三维框架结构 磁性

山西省基础研究计划项目山西省高等学校科技创新项目山西省高等学校教学改革创新项目

2023030212123562022L583J20221201

2024

人工晶体学报
中材人工晶体研究院

人工晶体学报

CSTPCD北大核心
影响因子:0.554
ISSN:1000-985X
年,卷(期):2024.53(10)