磺酸基团修饰的间苯二酚杯[4]芳烃对有机阳离子的包合作用  

Inclusion of organic cations by calix[4]resorcinarenes modified with sulfonic acid groups

作　　者：王晴 刘景龙[1] 孙梦 周新民 贾爱铨[1] 张千峰[1] Qing Wang;Jing-Long Liu;Meng Sun;Xin-Min Zhou;Ai-Quan Jia;Qian-Feng Zhang(Institute of Molecular Engineering and Applied Chemistry,Anhui University of Technology,Maanshan 243002,China)

机构地区：[1]安徽工业大学分子工程与应用化学研究所,马鞍山243002

出　　处：《中国科学：化学》2024年第3期396-404,共9页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:90922008)资助项目。

摘　　要：杯芳烃是第三代超分子化学的主要研究对象之一,其中间苯二酚杯[4]芳烃的功能化修饰在近几年受到了越来越多的关注.本文以间苯二酚为起始原料合成两例间苯二酚杯[4]芳烃,并在其C-2位以亚甲基为桥连引入磺酸基团合成间苯二酚杯[4]芳烃磺酸衍生物2a与2b,探究其与溶剂分子、有机铵盐的包合作用.通过X射线单晶衍射确定了2a与Me_4NCl、2b与Me OH均形成1:1的包合物,其中铵盐阳离子被2b二聚体所包裹.通过核磁氢谱研究,2b对Et_4NCl和n-Bu_4NCl的包合行为,结果表明铵盐阳离子的N~+头部嵌入杯芳烃头部亲水性四个磺酸基团中.通过紫外差光谱法作用研究了包合物吸光度与主客体分子浓度比的关系.检测了包合物2a·Me_4NCl催化合成异氰尿酸三缩水甘油酯的应用,发现其拥有良好的循环催化性能.Calix[4]resorcinarene,as an important branch of the third generation supramolecular compounds,calixarene,have received increasing attention for their functionalized modifications in recent years.In this paper,calix[4]resorcinarenes were synthesized by using resorcinol as the starting material,and calix[4]resorcinarene sulfonic acid derivatives 2a and 2b were synthesized by introducing sulfonic acid groups at their C-2 positions with methylene as a bridge link.The inclusion behavior of 2a and 2b towards solvent molecules and organic ammonium salts was studied.The molecular structures of 2a·Me4NCl and 2b·MeOH were determined by X-ray single-crystal diffraction,indicating their 1:1 inclusion formation.Of which,the ammonium cations were encapsulated by dimer of 2a in 2a·Me4NCl.The 1H NMR characterization was performed to investigate the inclusion of 2b with Et4NCl and n-Bu4NCl,the results showed that the N+head of ammonium salts are embedded to sulfonic acid groups of 2b.Ultraviolet(UV)spectrum was performed on studying the relationship of absorption of inclusion complex and concentration ratio of host and guest.Moreover,the catalytic effect of 2a·Me4NCl in the synthesis of triglycidyl isocyanurate was examined,and it was found to possess good catalytic properties.

关 键 词：芳烃 磺酸衍生物 主客体化学 

分 类 号：O641.3[理学—物理化学]