Liu Zhaona, Li Bing, Song Leqian, Zhang Huacheng
Medical School, Xi'an Peihua University Xi'an 710125 Shaanxi China
School of Chemical Engineering and Technology, Xi'an Jiaotong University Xi'an Shaanxi 710049 China
RSC Adv. 2022 Oct 3;12(43):28185-28195. doi: 10.1039/d2ra05118d. eCollection 2022 Sep 28.
To reserve planar chirality, enhance molecular recognition, and build advanced self-assemblies, hybrid macrocyclic hosts containing rigid pillar[]arene and flexible calix[]arene were designed, prepared and investigated for interesting applications. This review summarizes and discusses different synthetic strategies for constructing hybrid macrocyclic structures. Pillar[]arene dimer with rigid aromatic double bridges provided the possibility of introducing calix[]arene cavities, where the planar chirality was reserved in the structure of pillararene. The capacity for molecular recognition was enhanced by hybrid macrocyclic cavities. Interestingly, the obtained pillar[]arene-calix[]arene could self-assemble into "channels" and "honeycomb" in both the solid state and solution phase as well as donate the molecular architecture as the wheel for the formation of mechanically interlocked molecules, such as rotaxane. In addition, the pillar[]arene and calix[]arene could also be coupled together to produce pillar[]arene embeded 1,3-alternate and cone conformational calix[]arene derivatives, which could catalyze the oxidative polymerization of aniline in aqueous solutions. Except for building hybrid cyclophanes by covalent bonds, weak supramolecular interactions were used to prepare pillar[]arene-calix[]arene analogous composites with other pillar-like pillar[]pyridiniums and calix-like calix[]pyrroles, exhibiting reasonable performances in enhancing molecular recognition and trapping solvent molecules.
为了保留平面手性、增强分子识别并构建先进的自组装体，设计、制备并研究了含有刚性柱芳烃和柔性杯芳烃的杂化大环主体，以用于有趣的应用。本综述总结并讨论了构建杂化大环结构的不同合成策略。具有刚性芳族双桥的柱芳烃二聚体提供了引入杯芳烃空腔的可能性，其中平面手性保留在柱芳烃结构中。杂化大环空腔增强了分子识别能力。有趣的是，所得到的柱芳烃 - 杯芳烃在固态和溶液相中都能自组装成“通道”和“蜂窝”结构，并且能够提供分子结构作为形成机械互锁分子（如轮烷）的轮子。此外，柱芳烃和杯芳烃还可以耦合在一起，生成嵌入柱芳烃的1,3 - 交替和锥构象杯芳烃衍生物，它们能够催化苯胺在水溶液中的氧化聚合反应。除了通过共价键构建杂化环番外，还利用弱超分子相互作用制备了与其他柱状柱吡啶和杯状杯吡咯的柱芳烃 - 杯芳烃类似复合材料，这些材料在增强分子识别和捕获溶剂分子方面表现出合理的性能。
