中文摘要
设计合成人工分子机器和开关当今化学学科的前沿研究领域之一。本课题根据分子识别和分子自组装原理，设计合成了一系列结构新颖的大环主体分子，系统地研究了他们的超分子组装行为及其超分子组装体的结构与性质。在可控分子机器和分子开关研究方面取得了可喜的成果和新的重要进展。（1）合成了一系列新型侧臂冠醚，组装得到了一系列新型环状二聚轮烷；（2）发现了一种新型自身分子络合物。34-冠-10功能侧臂冠醚可通过分子内自识别，形成一种全新的"帆船型"自身络合物。通过溶液酸碱性的改变可调控其络合与解离过程，作为酸/碱控制的新型分子开关，有可能在基于34-冠-10的轮烷、索烃的分子机器控制方面得到广泛应用；（3）发现吡啶氮氧化物通过多重氢键协同作用和π-π叠加作用能与间苯二甲酰胺大环冠醚形成准轮烷，且该体系可作为新型可控的分子开关。预示组装体将可用于一系列新型轮烷、索烃的合成及相关分子机器的开发；（4）在二芳基大环冠醚的合成方法、双冠醚的合成、含丁二炔的新型大环冠醚和穴醚的合成与超分子组装等方面也取得了一系列研究成果。发展和丰富了超分子化学的内涵，拓展了超分子组装的应用范畴。
英文摘要
Design and synthesis of artificial molecular machines and switches has been a subject of intense study in recent years. In this project, we have designed and synthesized a series of novel macrocyclic host molecules. The self-assembly behaviours of these compounds, the structure and properties of the assemblies were investigated. Several new controllable and interesting molecular machines have been developed. These new findings include: (1) Several new cyclic rotaxane dimmers are achieved via self-assembly of novel functional lariat ethers; (2) A new type of self-complex, i.e a sailboat-like complex, was found by self-complexation of benzylammoniummethylene substituted bis(p-phenylene)-34-crown-10. Its decomplexation/recomplexation process can be controlled by acid-base stimuli. Using this self-complexing molecular switch to control the dethreading/rethreading of paraquat through the cavity of BPP34C10 is successfully demonstrated, implying it is useful for construction of novel rotaxane and catenane-based molecular machines. (3) Another important finding is that pyridine N-oxide as a new motif is capable of formation of [2]pseudorotaxane with amide macrocycle in solution and in the solid state, and the system can serve as a new controllable molecular switch with acid-base actuation. This finding bodes well for the extension of this motif to more complex supramolecular systems with interlocked [n]rotaxanes and [n]catenanes and for constructing new nanoscale molecular machines and devices. (4) A novel and high-yielding approach has been developed for synthesis of bisaryl crown ethers, diacetylene-incorporated crown ethers and cryptands, and valuable results are achieved for the applications of these new crown compounds in supramolecular assembly. The findings obtained in this research would be useful for creating advanced molecular devices and would further widen the scope of the chemistry.
结题摘要
设计合成人工分子机器和开关当今化学学科的前沿研究领域之一。本课题根据分子识别和分子自组装原理，设计合成了一系列结构新颖的大环主体分子，系统地研究了他们的超分子组装行为及其超分子组装体的结构与性质。在可控分子机器和分子开关研究方面取得了可喜的成果和新的重要进展。（1）合成了一系列新型侧臂冠醚，组装得到了一系列新型环状二聚轮烷；（2）发现了一种新型自身分子络合物。34-冠-10功能侧臂冠醚可通过分子内自识别，形成一种全新的"帆船型"自身络合物。通过溶液酸碱性的改变可调控其络合与解离过程，作为酸/碱控制的新型分子开关，有可能在基于34-冠-10的轮烷、索烃的分子机器控制方面得到广泛应用；（3）发现吡啶氮氧化物通过多重氢键协同作用和π-π叠加作用能与间苯二甲酰胺大环冠醚形成准轮烷，且该体系可作为新型可控的分子开关。预示组装体将可用于一系列新型轮烷、索烃的合成及相关分子机器的开发；（4）在二芳基大环冠醚的合成方法、双冠醚的合成、含丁二炔的新型大环冠醚和穴醚的合成与超分子组装等方面也取得了一系列研究成果。发展和丰富了超分子化学的内涵，拓展了超分子组装的应用范畴。