两个包含联苯三羧酸配体的铜(Ⅱ)和锰(Ⅱ)配合物的合成、晶体结构及磁性质

摘要

采用水热方法,用联苯三羧酸配体(H3dppa)和4,4'-联吡啶(4,4'-bipy)分别与CuCl2·2H2O和MnCl2·4H2O反应,合成了一个具有零维双核铜结构的配合物[Cu2(Hdppa)2(4,4'-bipy)(H2O)4]·4,4'-bipy· 6H2O (1)和一个基于双螺旋链单元的三维配位聚合物{[Mn3(μ5-dppa)2(4,4'-bipy)(H2O)2]·4H2O)n(2),并对其结构和磁性质进行了研究.结构分析结果表明2个配合物分别属于三斜和单斜晶系,P1和C2/c空间群.配合物1具有零维双核铜结构,而且这些双核铜单元通过O-H…O/N氢键作用进一步形成了三维超分子框架.而配合物2中存在一个双螺旋锰链单元,这些锰链单元又通过配体进一步连接成了三维结构.研究表明,配合物2中相邻锰离子间存在反铁磁相互作用.%Zero dimensional dinuclear copper(Ⅱ) coordination compound and 3D manganese (Ⅱ) coordination polymer,namely [Cu2(Hdppa)2(4,4'-bipy)(H2O)4]·4,4'-bipy·6H2O (1) and {[Mn3(μ5-dppa)2(4,4'-bipy)(H2O)2]·4H2O}n (2),have been constructed hydrothermally using H3dppa,4,4'-bipy (H3dppa=5-(3,4-dicarboxylphenyl)picolinic acid,4,4'-bipy=4,4'-bipyridine),and copper or manganese chlorides.Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system,space group P(1) or C2/c.In compound 1,one 4,4'-bipy ligand bridges neighboring Cu(Ⅱ) ions to form a discrete dinuclear copper(Ⅱ) structure.These Cu2 units are assembled to a 3D supramolecular framework through O-H …O/N hydrogen bond.In compound 2,neighboring Mn(Ⅱ) ions are bridged by the carboxylate groups ofμ5-dppa3-ligands,producing a double-helix Mn(Ⅱ) chain subunit.The adjacent double-helix chains subunits are further linked by the dppa3-blocks and 4,4'-bipy ligands into a 3D framework.Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn (Ⅱ) centers.