具有优良传导性能杂多酸复合物{[Co(H_2O)_8][H(H_2O)_3](HINO)_4(PW_(12)O_(40))}_n的合成,结构和性质研究  

A Good Proton-conductive Polyoxometalate Complex {[Co(H_2O)_8][H(H_2O)_3](HINO)_4(PW_(12)O_(40))}_n:Synthesis,Crystal Structure and Properties

作　　者：段显英[1,2] 郭利兵[1] 王建莉[1] 

机构地区：[1]河南省科学院化学研究所,郑州450002 [2]南京大学配位化学国家重点实验室,南京210093

出　　处：《化学学报》2013年第1期107-113,共7页Acta Chimica Sinica

基　　金：河南省基础与前沿技术研究计划(No.122300410090)资助~~

摘　　要：我们通过质子化水簇H+(H2O)3,过渡金属离子水簇[Co(H2O)8]2+,Keggin型结构[PW12O40]3-杂多阴离子和N-氧化吡啶-4-甲酸(HINO)的自组装成功地合成了一个质子传导无机-有机复合物.293 K的单晶结构分析表明化合物是一个具有大的1D通道的3D氢键网络,[PW12O40]3-以聚多阴离子链的形式填充于孔道中.热重分析结果表明此化合物在100℃以下比较稳定,结构没有发生改变,在200℃虽然失去了结晶水,但其结构还是比较稳定的.质子导电性能测试结果表明此化合物在温度为85～100℃范围内相对湿度为98%时的电导率达到1×10-3～2×10-3S cm-1,具有良好的导电性.通过实验结论,对质子传递的可能机理进行了推测.One organic/inorganic hybrid complex {[Co（H2O）8][H（H2O）3]（HINO）4（PWI2040）}n, was constructed by a self-assembly of H＋（H2O）3 clusters, [Co（H2O）8]2＋ clusters, [PWl2040]3- anions and isonicotinic acid N-oxide （H1NO）. It was characterized by X-ray diffraction analysis, elemental analysis, IR, TG, UV, XRD, proton conductivity analysis. In the synthetic procedure of title complex, a mixture of result heteropolyacid cobalt salts CoHPW12040.nH2O（90 mg, 0.03 mmol） and HINO （17 mg, 0.12 mmol） was dissolved in enough acetonitrile/water （1 ：1, V/V） to form a homogeneous solution. Finally, the solution was filtered and the solvent left to evaporate at room temperature. A week later, light red crystals appeared and were collected and dried in air after quickly being washed with water. Single-crystal X-ray diffraction analysis at 293 K showed that complex 1 crystallizes in orthorhombic crystal system, Pnnm, and there was exactly a three-dimensional （3D） hydrogen-bonded network with large one-dimensional （1D） channels, in which [PW12040]3- anions just filled in the 1D channels and self-assembled into poly-Keggin-anion chains. The result of the UV spectra indicates that the saturated aqueous concentration of 1 is ca. 10-s mol/L and it is insoluble in water. Thermogravimetric analysis shows no weight loss in the temperature range of 20～ 100℃, indicating that all water molecules in the structure are not easily lost below 100 ℃. The powder X-ray diffraction data exhibits that although crystallized water molecules are lost at 200℃, the evacuated complex has the same structure as the single-crystal of 1. Moreover, the powder sample after the proton-conductive measurement has the same supramolecular framework as that of complex 1. Interestingly, the title complex was characterized by a satisfactory ionic conductivity （1 × 10-3～2 × 10-3 S,cm-1） in the temperature range of 85 to 100℃ only. The mechanism of proton conduction of the title complex is, expected to be sim

关 键 词：杂多酸 晶体结构 超分子复合物 传导材料 N-氧化吡啶-4-甲酸 

分 类 号：O614.812[理学—无机化学]