杂多酸钾杯芳烃衍生物的合成、结构及电化学性质

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]4HPW12O40]3·CH3COCH3(1), L-K2]2·SiW12O40]·2CH2Cl2·CHCl3(2)和L-K1.5]2PMo12O40]·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.

Synthesis, Structure and Electrochemical Property of Calixarene Potassium Polyoxometalates

One inorganic-organic hybrid and two host-guest complexes were synthesized from calix4] 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.