由于具有三维空腔结构及良好的应用前景,穴醚逐渐成为超分子研究领域的热点之一.近年来,我们课题组设计合成了一系列基于双间苯-32-冠-10穴醚主体分子,并利用这些穴醚分子构筑了不同的超分子组装体.首先,将双硫代四硫富瓦烯(STTFS)引入到穴醚的第三个臂上,成功构筑了具有氧化还原响应性的穴醚主体分子.该穴醚与客体间的解离-穿环过程可以利用STTFS的氧化态来进行控制;其次,设计合成了两种含有P=O官能团桥连的穴醚,在固态结构中得到了近似线型和Z字型的不同超分子聚[2]准轮烷;最后,合成了具有两种不同性质空腔的柱[5]芳烃稠合穴醚主体分子,该穴醚通过正交作用同时络合两个不同的客体分子.基于两种不同主客体作用力,我们构筑了一种新型的超分子聚合物.以上研究为分子器件和超分子材料的进一步研究奠定了良好的基础.
Crown ether-based cryptands have attracted much attention not only because of their 3D spatial architectures but also due to their good application prospects. In recent years, our group has prepared a series of supramolecular assemblies containing bis(m-phenylene)-32-crown-10-based cryptands. Firstly, by attaching a bisthiotetrathiafulvalene(STTFS) unit to the third arm of the cryptand, a redox-switchable cryptand was synthesized successfully. It was found that the dethreading-rethreading processes between this cryptand and the guests could be well-controlled in different redox states owing to the specific redox-active properties of the STTFS unit. Secondly, two types of cryptand-based host-guest complexes were also constructed successfully, in which P=O functional groups were located at the different positions of the third arms. These two new cryptands were capable of forming [2]pseudorotaxanes with the paraquat guest both in solution and in the solid state. Moreover, the generated [2]pseudorotaxanes could further self-assemble into supramolecular poly[2]pseudorotaxanes in the solid state. Interestingly, it was found that two different types of supramolecular poly[2]pseudorotaxanes were formed in almost linear and zigzag shapes in the solid state. Thirdly, a pillar[5]arene-fused cryptand with two different cavities was also synthesized successfully. The cavity of BMP32C10-based cryptand in this tricyclic host molecule could selectively interact with the paraquat guest. The complexation behaviours between host and two different guest species were selective, and more importantly, in an orthogonal fashion. And based on this orthogonal self-assembly of two host-guest interactions, a novel type of supramolecular polymer was constructed easily and conveniently. These above researches of cryptands will provide the diverse motifs for the constructions of molecular devices and supramolecular materials.