基于二吡啶二酰胺的Ni(Ⅱ)金属有机框架的合成、结构和磁性

Syntheses,Crystal Structures and Magnetic Properties of 2D Nickel(Ⅱ) Metal-Organic Frameworks Based on N,N’-bis-(3-pyridyl)isophthalamide and N,N’-bis-(3-pyridyl)terephthalamide

在水热条件下,分别基于配体N,N′-双(3-吡啶基)-间苯二甲酰胺(3-bpipa)和N,N′-双(3-吡啶基)-对苯二甲酰胺(3-bptpa),合成了具有二维格子结构的镍(Ⅱ)MOFs:[Ni(3-bpipa)(1,3-bdc)(H_(2)O)]·4H_(2)O(1)和[Ni(3-bptpa)(5-Hhip)(H_(2)O)]·3.5H_(2)O(2),并进行了红外光谱、X-射线单晶衍射和磁学表征.在配合物1和2中,Ni(Ⅱ)均处于Ni O_(4)N_(2)扭曲的八面体配位环境,相邻的Ni(Ⅱ)…Ni(Ⅱ)距离分别为1.24467(37)和1.0195(21)nm.仅考虑单个Ni(Ⅱ)(S=1)离子的贡献,并利用分子场近似处理Ni(Ⅱ)离子间的磁相互作用,对配合物1和2在16-300 K的磁化率数据进行分析,最佳拟合结果分别为:z J′=-0.88 cm^(-1),g=2.09和z J′=-1.04 cm^(-1),g=2.21,表明相邻Ni(Ⅱ)离子通过桥连配体传递较弱的反铁磁相互作用.

Based on N,N’-bis-(3-pyridyl)terephthalamide (3-bptpa) and N,N’-bis-(3-pyridyl)isophthalamide(3-bpipa),two Ni(Ⅱ) Metal-Organic Frameworks,[Ni(3-bpipa)(1,3-bdc)(H_(2)O)]·4H_(2)O (1,3-H_(2)bdc=1,3-benzenedicarboxylic acid)(1) and[Ni(3-bptpa)(5-Hhip)(H_(2)O)]·3.5H_(2)O (5-H_(3)hip=5-hydroxyisophthalic acid)(2),with 2D grid-like structure were hydrothermally synthesized and characterized by X-ray crystallography,IRspectra,and magnetic measurements.In complexes 1 and 2,Ni(Ⅱ) was located in a distorted octahedral coordination environment of Ni O_(4)N_(2),and the distances between adjacent Ni(Ⅱ) cations were 1.244 67(37) and1.019 5(21) nm,respectively.Considering the contribution of single Ni(Ⅱ)(S=1) ion,and using molecular field approximation to process the magnetic interaction between Ni(Ⅱ) ions,the magnetic susceptibility data of complexes 1 and 2 at 16-300 K were analyzed.The best fitting results were z J′=-0.88 cm^(-1),g=2.09 and z J′=-1.04 cm^(-1),g=2.21,respectively,indicating that adjacent Ni(Ⅱ) ions transfer weak antiferromagnetic interactions through the bridging ligands.