由联苯三羧酸配体构筑的零维四核镍(Ⅱ)配合物和一维锰(Ⅱ)配位聚合物的合成、晶体结构及磁性质

摘要

采用水热方法,用2种联苯三羧酸配体biphenyl-2,5,3'-tricarboxylate acid(H3bptc)和2-(4-carboxypyridin-3-yl)terephalic acid(H3cptc)以及菲咯啉(phen)或2,2'-联吡啶(2,2'-bipy)分别与NiCl2·6H2O和MnCl2·4H2O反应,合成了一个具有零维四核镍结构的配合物[Ni2(μ3-Hbptc)(Hbptc)(phen)3(H2O)]2·4H2O(1)和一个基于三核锰单元的一维链状配位聚合物([Mn3(μt4-cptc)2(2,2'-bipy)2(H2O)4]·2H2O}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个配合物均属于三斜晶系,P(1)空间群.配合物1具有零维四核镍结构,而且这些四核镍单元通过O-H…O氢键作用进一步形成了三维超分子框架.而配合物2中存在一个中心对称的三核锰单元,这些三核锰单元又通过配体进一步连接成了一维链.研究表明,配合物1和2中相邻金属离子间存在反铁磁相互作用.%A 0D tetranuclear nickel(Ⅱ) coordination compound and a 1D manganese(Ⅱ) coordination polymer,namely [Ni2(μ3-Hbptc)(Hbptc)(phen)3(H2O)]2·4H2O (1) and {[Mn3(μ4-cptc)2(2,2'-bipy)2(H2O)4]·2H2O}n (2),have been constructed hydrothermally using H3bptc (H3bptc=biphenyl-2,5,3'-tricarboxylate acid),H3cptc (H3cptc=2-(4-carboxypyridin-3-yl)terephalic acid),phen (phen=l,10-phenanthroline) or 2,2'-bipy (2,2'-bipy=2,2'-bipyridine),and nickel or manganese chlorides.Single-crystal X-ray diffraction analyses revealed that both compounds crystallize in the triclinic system,space group P(1).In compound 1,twoμ3-Hbptc2-ligands bridge alternately neighboring Ni(Ⅱ) ions to form a discrete tetranuclear nickel(Ⅱ) structure.These Ni4 units are assembled to a 3D supramolecular framework through O-H… O hydrogen bond.In compound 2,three neighboring Mn(Ⅱ) ions are bridged by four differentμ4-cptc3-ligands,giving rise to a centrosymmetric trinuclear Mn(Ⅱ) subunit.The adjacent Mn3 subunits are further linked by the cptc3-blocks into a 1D chain.Magnetic studies for compounds 1 and 2 demonstrate an antiferromagnetic coupling between the adjacent metal centers.CCDC:1588394,1;1588395,2.