基于杯[4]芳烃与多酸设计合成主客体化合物及性能研究

项目名称： 基于杯[4]芳烃与多酸设计合成主客体化合物及性能研究

项目编号： No.U1304210

项目类型： 联合基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 刘雷雷

作者单位： 安阳师范学院

项目金额： 30万元

中文摘要： 采用主客体化合物来进行催化研究总是不断激起人们的兴趣，但筛选出具有特殊结构的主客体化合物成为高效特别是高选择性的催化剂是一个难题。因此，本项目拟设计合成杯芳烃上沿是刚性吡啶基或苯甲酸基的杯[4]芳烃和上沿是柔性(由亚甲基桥联)氰基或羧基[？(CH2)nCN/COOH，n=0，1，2]的杯[4]芳烃；利用这类配体自身的结构特点与多酸(Keggin、Dawson和Anderson等)和金属离子自组装，可控的得到具有多孔结构的主客体化合物；系统研究它们的合成规律，进而可控的合成具有不同孔道大小和类型的配合物；测定它们对催化烯烃环氧化的性能；考察配体上官能团的配位性、柔性与刚性连接基团和多酸的类型对配合物结构和其催化性能的影响；研究这些配合物孔道大小和类型的不同对催化烯烃环氧化反应中底物的影响，使这类配合物能够达到最佳的催化活性和区域选择性。这种合成方法为合成其它高效高选择性的催化剂提供了新思路。

中文关键词： 杯[4]芳烃；多金属氧酸盐；主客体化合物；组装；催化

英文摘要： Rencently, plenty of host-guest complexs were employed as catalysts have been paied much attention. However, how to screen to such componds containing specific ligands as the catalysts with good efficiency and high selectivity has been a long term challenge. So, we delicatuely designed and synthesized a series of calix[4]arene derivatives with rigid pyridine/benzoxy groups and flexible cyano/carboxyl groups [？(CH2)nCN/COOH, n = 0, 1, 2] at the upper-rim of calix[4]arenes. Such calix[4]arene ligands with inherent cone conformation assembly of polyoxometalates (Keggin, Dawson and Anderson) and metal ions afforded kinds of porous host-guest complexs. And the size and species of channels of above compounds could be controlled synthesized through regulating the reaction conditions. Choosing parts of these host-guest compounds catalyze epoxidation of olefins and considering coordination effect, spacers of calix[4]arenes ligands and the species polyoxometalates how to affect the structures of metal complexes and catalytic performance. Moreover, through of regulating the size of channels of the complexes achieve the best catalytic activity and selectivity. This synthetic methodology provides a new route to produce other catalysts with good efficiency and high selectivity.

英文关键词： Calix[4]arene；Polyoxometalate；Host-Guest complexes；Assembly；Catalysis