含有Cu2O2亚单元的一维Cu(Ⅱ)梯形链状配位聚合物的合成、晶体结构及磁性研究

摘要

以4,4'-bpy为桥联配体、多配位点Schiff碱为辅助配体与Cu(Ⅱ)离子进行自组装,获得了由四边形Cu2O2为亚结构单元构成的结构新颖的梯形链状Cu(Ⅱ)配位聚合物,其组成分别为[Cu2(HL1)2(4,4'-bpy)](ClO4)2}n(1)和[Cu2(L2)2(4,4'-bpy)]n(2)[其中4,4'-bpy=4,4'-联吡啶,H2L1=2-((1-羟基丙醛-2-基)亚氨基)甲基)苯酚,H2L2=2-((2-羟基-3-甲氧基亚苄基)氨基)丙酸].通过FTR、元素分析、TGA及X射线单晶衍射分析等对配合物进行了表征.2种配位聚合物的结构多样性表明,Schiff碱辅助配体可以调节一维配位聚合物的拓扑结构.变温磁化率测定及磁性分析结果表明,配位聚合物1和2中通过酚氧基桥联的Cu(Ⅱ)离子间存在较强的铁磁耦合作用,其磁耦合参数分别为J=37.40 cm-1 (1)和J=12.70 cm-1 (2).%Two new ladder-like chain Cu(Ⅱ) coordination polymers containing quadrangular Cu2O2 subunits,formulated as {[Cu2(HL1)2(4,4'-bpy)](ClO4)2}n (1),[Cu2(L2)2(4,4'-bpy)]n (2),and [4,4'-bpy =4,4'-bipyridine,H2L1=2-(((1-hydroxypropan-2-yl)imino)methyl)phenol,H2L2=2-((2-hydroxy-3-methoxybenzylidene)amino) propanoic acid],have been synthesized using self-assembled method by reactions of bridge ligand 4,4'-bpy with Cu(Ⅱ) ions in the presence of different Schiff base ligands.These complexes were characterized by Fourier transform infrared (FTIR) spectroscopy,elemental analysis,thermogravimetric analysis (TGA) and single-crystal X-ray diffraction analysis.The structural diversity of two coordination compounds indicates that the structures can be tuned by modification of Schiff base ligands.In addition,variable-temperature magnetic analysis of 1 and 2 shows that a ferromagnetic coupling interaction were mediated through the phenolate bridge between two Cu(Ⅱ) ions in the subunits (binuclear core) and the parameters are given as J =37.40 cm1 for 1 and J =12.70 cm1 for 2.