镍螺旋化合物及其杂银配位聚合物的设计合成与结构

摘要

Two molecular clips with flexible bis-tridentate coordination sites, di (2-pyridylcarbaldehyde)-6,6'-dicarboxylic acid hydrazone-2,2'-bipyridine (H2L1) and di(2-acetylpyridyl)-6,6'-dicarboxylic acid hydrazone-2,2'-bipyridine (H2L2) have been prepared. Dinuclear double-stranded helicate Ni2(HL1)2(PF6)(BF4)(CH3OH)(H2O)2(1)and Ni2(HL2) (H2L2)(ClO4)3(C2H5OH)(CH3OH)(H2O)3(2)based on the ligands, H2L1 and H2L2 respectively, have been synthesized, their crystal structures were determined by X-ray diffraction method. Meanwhile, the assembly between the modulated ligand, di(2-pyrazinecarbaldehyde)-6,6'-dicarboxylic acid hydrazone-2,2'-bipyridine (H2L3)and mixed metal salts of nickel and silver yields a 1D coordination polymer Ni2Ag2(HL3)2(ClO4)2(CH3CN)3 (3). The crystal structure revealed that, in the compound 3, molecular box as metallosupramolecular secondary building units, can be interconnected via the external Ag-N coordination to construct metallosupramolecular aggregate.Another intriguing structure feature of the compound 3 in the solid state is that it forms two-dimensional porous frameworks through the stacking of the 1D aggregated molecular box, in which counter anions and guest solvent molecules are resided. CCDC: 640381, 1, 640382, 2, 640383, 3.%采用两个易扭转异构的双三齿有机配体,双吡啶二甲基-6,6'-二酰肼-2,2'-连吡啶(H2L1)和双吡啶二乙基-6,6'-二酰肼-2,2'-连吡啶(H2L2),和金属镍离子组装得到2个金属螺旋体(helicate),Ni2(HL1)2(PF6)(BF4)(CH3OH)(H2O)2(1)和Ni2(HL2)(H2L2)(ClO4)3(C2H5OH)(CH3OH)H2O)3(2),并测定了它们的晶体结构.同时由配体H2L3出发,通过逐级组装的方法,得到一个镍-银杂金属的配位聚合物Ni2Ag2(HL3)2(ClO4)2(CH3CN)3(3).单晶结构表明,配位聚合物3中配体H2L3首先与镍离子组装成分子盒化合物(molecular box),该结构单元进一步通过Ag离子与分子盒外围N原子配位,使分子盒互相串连成一维配位聚合物3,分子盒聚集体沿c方向伸展成一维链结构,链与链之间相互平行,进一步堆积成二维孔道结构.