高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

杂多酸钾杯芳烃衍生物的合成、结构及电化学性质

刘巨涛1,2, 刘晓伟1, 范圣第1, 李德谦2   

    1. 大连民族学院生物技术与资源利用国家民委-教育部重点实验室, 大连 116600;
    2. 中国科学院长春应用化学研究所, 长春 130022
  • 收稿日期:2006-09-02 修回日期:1900-01-01 出版日期:2007-07-10 发布日期:2007-07-10
  • 通讯作者: 刘巨涛

Synthesis, Structure and Electrochemical Property of Calixarene Potassium Polyoxometalates

LIU Ju-Tao1,2*, LIU Xiao-Wei1, FAN Sheng-Di1, LI De-Qian2   

    1. Key Laboratory of Biotechnology & Bioresources Utilization the State Ethnic Affairs Commission-Ministry of Education, Dalian Nationalities University, Dalian 116600, China;
    2. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  • Received:2006-09-02 Revised:1900-01-01 Online:2007-07-10 Published:2007-07-10
  • Contact: LIU Ju-Tao

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被引次数

7

摘要：

以3种Keggin型杂多酸钾和杯芳烃四乙酸乙酯衍生物(C60H80O12, L)为原料, 合成了一个杯-簇型无机-有机杂化配合物和两个杯-簇-杯型主-客体配合物: [L-K1.5]4[HPW12O40]3·CH3COCH3(1), [L-K2]2·[SiW12O40]·2CH2Cl2·CHCl3(2)和[L-K1.5]2[PMo12O40]·2CHCl3(3). 通过元素分析、IR、TG-DTA和X射线衍射等手段对配合物进行了表征, 测得了其晶体结构. 研究结果表明, 配合物1中杯芳烃衍生物钾配阳离子与Keggin型磷钨酸多阴离子属典型的无机-有机杂化结构. 钾离子完全进入杯芳烃衍生物的空腔, 并与氧原子形成配位键, 多阴离子则表现为相对孤立的阴离子簇, 其金属氧簇结构基本保持不变. 配合物2和3的结构中杯芳烃衍生物钾配阳离子和多酸阴离子具有杯-簇-杯排列方式. 两个钾离子以配位串的方式进入杯芳烃衍生物的空腔, 并与氧原子形成配位键, 多阴离子簇则位于两个配阳离子中间, 对发生客居的钾离子串起着约束的作用. 电化学结果表明, 配合物1在1.0 mol/L H2SO4溶液中的氧化还原峰电流与扫速的平方根成线性关系, 电极反应为扩散控制过程; 配合物2和3在2.0 mol/L H2SO4溶液中的氧化还原峰电流与扫速成线性关系, 为表面控制过程. 说明电极反应与配合物的结构密切相关.

关键词: 杂多酸钾, 杯芳烃衍生物, 无机-有机杂化, 主-客体, 晶体结构, 电化学性质

Abstract:

One inorganic-organic hybrid and two host-guest complexes were synthesized from calix arene tetra acetic ether derivative(C60H80O12, L) and potassium polyoxometalates. The structures of the complexes were characterized with the elemental analysis, IR, TG-DTA and X-crystallographic. X-ray crystallographic studies reveal the formation of an ionic crystal, which contains a calix-cluster and calix-cluster-calix line array, and belongs to a typical inorganic-organic hybrid(complex 1) or has a host-guest structure(complex 2 and 3) . The results of cyclic voltammograms at different scanning rates showed that the anode peak current of complex 1 was proportional to the square root of the scanning rate and the charge transfer process was controlled by pervasion. The anode peak current of complexes 2 and 3 was proportional to the scanning rate and the charge transfer process was controlled by the surface. The results suggest that there are consanguineous relationship between the anode reaction and the structure.

Key words: Potassium polyoxometalate, Calixarene derivative, Inorganic-organic hybrid, Host-guest, Crystal structure, Electrochemical property

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