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《Acta Chimica Sinica》 2016-01
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Design and Construction of Supramolecular Assemblies Containing Bis(m-phenylene)-32-crown-10-based Cryptands

Wang,Qi;Cheng,Ming;Cao,Yihan;Jiang,Juli;Wang,Leyong;Key Laboratory of Mesoscopic Chemistry of MOE,School of Chemistry and Chemical Engineering,Nanjing University;  
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.
【Fund】: 国家自然科学基金(Nos.21472088;91227106)资助~~
【CateGory Index】: O641.3
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