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镍螺旋化合物及其杂银配位聚合物的设计合成与结构
引用本文:吴大雨,黄薇,李庚,谢黎霞,段春迎,孙巧珍,孟庆金.镍螺旋化合物及其杂银配位聚合物的设计合成与结构[J].无机化学学报,2007,23(7):1129-1136.
作者姓名:吴大雨  黄薇  李庚  谢黎霞  段春迎  孙巧珍  孟庆金
作者单位:南京大学化学化工学院,配位化学研究所,配位化学国家重点实验室,南京,210093
摘    要: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。

关 键 词:螺旋    分子盒    多孔结构    逐级组装    配位聚合物
文章编号:1001-4861(2007)07-1129-08
修稿时间:2007-03-162007-05-10

Nickel Helicates and Hybrid Silver Coordination Polymer: Design, Synthesis and Structure Characterization
WU Da-Yu,HUANG Wei,LI Geng,XIE Li-Xi,DUAN Chun-Ying,SUN Qiao-Zhen and MENG Qing-Jin.Nickel Helicates and Hybrid Silver Coordination Polymer: Design, Synthesis and Structure Characterization[J].Chinese Journal of Inorganic Chemistry,2007,23(7):1129-1136.
Authors:WU Da-Yu  HUANG Wei  LI Geng  XIE Li-Xi  DUAN Chun-Ying  SUN Qiao-Zhen and MENG Qing-Jin
Institution:School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093,School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093,School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093,School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093,School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093,School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093 and School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093
Abstract: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.
Keywords:helicate  molecular box  pore structure  hierachical self-assembly  coordination polymer
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