基于希夫碱配体的线型三核过渡金属配合物的合成、晶体结构及磁学性质研究

Schiff-base based linear trinuclear transition metal complexes: synthesis,crystal structures and properties

以邻羟基苯乙酮和1,3-丙二胺为原料,合成了平面四齿螯合型希夫碱有机配体。利用此希夫碱配体分别与镍、铜、锌的水合醋酸盐在甲醇和乙腈的混合溶剂中反应,得到了三个希夫碱金属配合物Ni_3(L)_2(CH_3COO)_2]·2CH_3CN·4H_2O(1),[Cu_3(L)_2(CH_3COO)_2]·CH_3CN·2H_2O(2)and[Zn_3(L)_2(CH_3COO)_2]·2CH_3CN(3)。配合物1-3用元素分析、红外光谱和X-射线单晶衍射进行了表征。单晶结构分析表明,配合物1结晶于单斜晶系,而配合物2和3是同构的,属于三斜晶系。这三个配合物具有类似的线型三核结构,含有两种晶体学独立的金属离子,其配位环境分别为六配位变形八面体和五配位四方锥的几何构型。配合物1和2的变温磁化率测量表明,金属离子之间存在反铁磁相互作用。

Three new transition metal complexes with the formula[Ni 3(L)2(CH 3COO)2]·2CH 3CN·4H 2O(1),[Cu 3(L)2(CH 3COO)2]·CH 3CN·2H 2O(2)and[Zn 3(L)2(CH 3COO)2]·2CH 3CN(3)have been obtained by the reactions of the tetra-dentate Schiff-base ligand 2,2’-(proane-1,3-diylbis(nitrilo(phenylmethylyidiene)))diphenol,which can be obtained by the condensation of 2-hydroxy acetophenone with 1,3-diaminopropane,with[Ni(CH 3COO)2]·4H 2O,[Cu(CH 3COO)2]·H 2O and[Zn(CH 3COO)2]·2H 2O in MeOH/CH 3CN,respectively.The three complexes have been characterized by element analysis,IR-spectra and X-ray diffraction.The X-ray structure determination reveals that the complex1crystallizes in monoclinic system,while complexes2and3belong to triclinic system.All the three complexes are with similar linear trinuclear core structure,in which the coordination spheres for the two kinds of the metal atoms are six-coordinated distorted octahedron and five-coordinated tetragonal pyramid,respectively.Investigation over the magnetic susceptibilities of the complexes1and2shows the antiferromagnetic interaction between the Ni or Cu ions.