基于二苯并24-冠-8桥联双柱[5]芳烃的线性和网状超分子聚合物

Linear and Cross-Linked Supramolecular Polymers Based on a Dibenzo-24-crown-8 Bridged Pillar[5]arene Dimer

设计合成了一种二苯并24-冠-8桥联双柱[5]芳烃杂交主体1.利用含有2个5-(1,2,3-1H-三氮唑基)戊腈(TAPN)中性键合位点的双主题客体2与主体1中的柱[5]芳烃空腔的强络合构筑了AA/BB型的线性超分子聚合物.进而利用桥链冠醚部分与双主题二级铵盐客体3主客体包结自组装制备了三组分网状的超分子聚合物.通过对线性和网状聚合物进行1H NMR、黏度、DOSY、SEM等表征,结果表明超分子自组装体的形成呈现浓度依赖性,其线型超分子聚合物在氯仿/丙酮中(V∶V=4∶1)的溶剂中临界聚集浓度(CPC)为28 mmol/L.此研究设计了一种利用多次主客体相互作用构建高分子量聚合物的方法,为超分子聚合物的发展开辟了一条新的途径.

One hybrid host molecule of dibenzo-24-crown-8 bridged pillar[5]arene dimer(1)was designed and synthesized.The combination of host 1 and ditopic guest 2 containing two 5-(1H-1,2,3-triazol-1-yl)pentanenitrile(TAPN)binding sites could afford linear AA/BB-type supramolecular polymers based on TAPN?pillar[5]arene recognition motif.Further introduction of ditopic guest 3 containing two secondary ammonium parts yields cross-linked supramolecular polymers through the host-guest inclusion between dibenzo-24-crown-8 and secondary ammonium salt.The supramolecular polymers were characterized by various techniques such as 1H NMR,viscosity,DOSY and SEM,indicating that the formation of these supramolecular polymer was concentration-dependent.The critical polymerization concentration(CPC)of the formation of linear supramolecular polymers in chloroform/acetone(V:V=4:1)solutions is 28 mmol/L.This work provides a new strategy for the fabrication of novel supramolecular aggregates based on orthogonal host-guest interactions of hybrid macrocycles.