氧杂杯[4]芳烃的功能化和自组装

Oxacalixarenes, an important class of heterocalixarenes, have attracted increasing interest in recent years due to the unique feature of bridging oxygen atoms. As reported by us before, oxacalix[4]arenes with four -NO2 groups and four -COOMe groups were synthesized and found to self-assemble into a novel nanotoroidal tubule in solid state. In this project, further derivation on the parent skeleton was pursued. Eight hydroxyl substitued oxacalix[4]arenes are designed, which might be found great potential applications in supramolecular chemistry, especially in constructing specific self-assembled supramolecular architectures, due to the strong hydrogen bonding ability of the -OH groups. Hydrogen bonding is a particularly attractive tool for assembling supramolecular cages or tubules because of its directional and reversible nature. Besides hydroxyl group, carboxyl or sulfonate groups also show their strong hydrogen bonding interactions with other guests such as guanidinium. On the other hand, carboxyl or sulfonate groups can also afford their self-assembly in aqueous media. Therefore, in this project, amphiphilic oxacalix[4]arenes with four hydroxyl groups and four carboxyl or sulfonate groups, and water-soluble oxacalix[4]arenes with eight carboxyl or sulfonate groups are designed and expected to self-assemble into supramolecular architectures with spherical and tubular morphologies..Nanosized cage compounds have attracted considerable attention for potential applications such as storage, recognition, delivery and catalysis. Herein, we design a series of molecular cages based on oxacalix[4]arenes. In the preparation, when the resorcinol moiety was replaced by other units such as four -OH substitued oxacalix[4]arenes, or six -OH substituted compounds, oxacalix[4]arenes-based cages may be synthesized in a single step, which provides a new platform for oxacalix[4]arenes and their host-guest chemistry.

本申请课题以氧杂杯芳烃大环主体为骨架，构筑一系列含多取代位点的功能化氧杂杯[4]芳烃。通过引进硝基、酯基、烷氧基等基团，进一步转化合成八羟基氧杂杯[4]芳烃，基于羟基的氢键作用有望构筑纳米尺度的分子胶囊或管道组装体；设计合成两亲性的四羟基四羧基（或磺酸基）氧杂杯[4]芳烃以及水溶性的八羧基（或磺酸基）氧杂杯[4]芳烃，基于这类功能基团的氢键以及金属配位作用在水溶液中构筑纳米尺度的超分子拓扑结构，例如多面体，球体或管道组装体等；同时在前期合成基础上利用进一步的亲核取代反应预期得到更复杂的笼状氧杂杯[4]芳烃，例如三环氧杂杯[4]芳烃和五环氧杂杯[4]芳烃。.本项目的研究能丰富与发展氧杂杯芳烃这一研究领域，通过超分子自组装的手段有望拓展氧杂杯芳烃类大环主体在纳米材料方面的应用，为新材料的研制提供新的思路和平台。

柱芳烃是当前快速发展的一类新型大环主体。该类大环具有丰富的衍生位点以及柱状的结构特点，进而显示出丰富的主客体络合作用以及广阔的应用空间。本课题由对氧杂杯[4]芳烃的功能化扩展为对新型大环主体的衍生化和应用研究。主要内容有：.(1) 将咔唑引入杂杯芳烃，成功合成了一类新型的氮杂杯[2]咔唑[2]芳烃；(2) 基于水溶性柱芳烃的主客体络合作用实现了银纳米粒子的可控自组装；(3) 基于水溶性柱[5]芳烃的识别作用在水中实现了棒-核两亲性分子的形貌可控自组装；(4) 基于水溶性柱[5]芳烃与10-甲基碘的识别作用构筑了检测紫精和氰化物的荧光传感器；(5) 基于水溶性柱[10]芳烃的识别作用实现了最低临界共溶温度（LCST）的响应性；(6) 在溶液和固态下基于单乙醚烷氧基衍生化的柱[5]芳烃构筑了超分子聚合物；(7) 制备了一类水溶性离子液柱[6]芳烃，并研究了其与对羟基苯甲酸钠的主客体络合作用。