A Good Proton-conductive Polyoxometalate Complex {[Co(H2O)8][H(H2O)3](HINO)4(PW12O40)}n: Synthesis, Crystal Structure and Properties

doi:10.6023/A12050254

Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (01): 107-113.DOI: 10.6023/A12050254 Previous Articles Next Articles

Article

具有优良传导性能杂多酸复合物{[Co(H₂O)₈][H(H₂O)₃](HINO)₄(PW₁₂O₄₀)}_n的合成, 结构和性质研究

段显英^a,b, 郭利兵^a, 王建莉^a

a 河南省科学院化学研究所郑州 450002;
b 南京大学配位化学国家重点实验室南京 210093

投稿日期:2012-05-29 发布日期:2012-12-10
通讯作者: 段显英 E-mail:dxynumber@163.com
基金资助:
项目受河南省基础与前沿技术研究计划(No. 122300410090)资助.

A Good Proton-conductive Polyoxometalate Complex {[Co(H₂O)₈][H(H₂O)₃](HINO)₄(PW₁₂O₄₀)}_n: Synthesis, Crystal Structure and Properties

Duan Xianying^a,b, Guo Libing^a, Wang Jianli^a

a Institute of Chemistry, Henan Academy of Sciences, Zhengzhou 450002, China;
b State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China

Received:2012-05-29 Published:2012-12-10
Supported by:
Project supported by Henan Province (No. 122300410090).

1. A Good Proton-conductive Polyoxometalate Complex {[Co(H₂O)₈][H(H₂O)₃](HINO)₄(PW₁₂O₄₀)}_n: Synthesis, Crystal Structure and Properties.PDF(153KB)

Abstract

One organic/inorganic hybrid complex {[Co(H₂O)₈][H(H₂O)₃](HINO)₄(PW₁₂O₄₀)}_n, was constructed by a self-assembly of H⁺(H₂O)₃ clusters, [Co(H₂O)₈]²⁺ clusters, [PW₁₂O₄₀]^3- anions and isonicotinic acid N-oxide (HINO). 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 CoHPW₁₂O₄₀·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 [PW₁₂O₄₀]^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^-5 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 similar to that of the vehicle mechanism, that is, the direct diffusion of additional protons with water molecules (Grotthuss mechanism).

Key words: polyoxometalate, crystal structure, supramolecular complex, conducting materials, isonicotinic acid N-oxide

Cite this article

Duan Xianying, Guo Libing, Wang Jianli. A Good Proton-conductive Polyoxometalate Complex {[Co(H₂O)₈][H(H₂O)₃](HINO)₄(PW₁₂O₄₀)}_n: Synthesis, Crystal Structure and Properties[J]. Acta Chimica Sinica, 2013, 71(01): 107-113.

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具有优良传导性能杂多酸复合物{[Co(H₂O)₈][H(H₂O)₃](HINO)₄(PW₁₂O₄₀)}_n的合成, 结构和性质研究

A Good Proton-conductive Polyoxometalate Complex {[Co(H₂O)₈][H(H₂O)₃](HINO)₄(PW₁₂O₄₀)}_n: Synthesis, Crystal Structure and Properties

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具有优良传导性能杂多酸复合物{[Co(H2O)8][H(H2O)3](HINO)4(PW12O40)}n的合成, 结构和性质研究