【作者】 张静；

【导师】 强琚莉； 王乐勇；

【作者基本信息】 南京大学 ， 有机化学， 2018， 硕士

【摘要】 作为超分子化学的研究基础,一代又一代的大环主体被成功合成出来。这些大环主体能与某些具有特殊性能的客体快速有效地结合,主客体之间通过分子间弱的相互作用来构筑超分子化合物。准轮烷和轮烷型分子就是通过这种大环与客体间的主客体作用构筑的典型的分子机器,准轮烷由轴分子和大环主体构成,其中轴分子通过分子间作用力可以被包含在大环的空腔内。轮烷是以准轮烷为基础,在轴分子的两端引入两个大的封端基团来使大环不会从轴上脱落。通过对准轮烷和轮烷主客体作用机理的研究,使得超分子在生命科学与智能材料等方面越来越受到关注。由此,本文基于传统的冠醚和穴醚,成功的构筑了准轮烷型的超分子聚合物和酸碱可控的荧光分子开关。第一章,概述超分子化学、冠醚和穴醚的发展及应用,并着重介绍了基于冠醚和穴醚的准轮烷型分子机器,同时还举例介绍了其在聚合物、离子识别、分子开关等方面的应用。第二章,我们将传统的32-冠-10冠醚以及24-冠-8冠醚通过酰胺键桥联,成功合成了一种不对称四臂穴醚。在该四臂穴醚中,既包含有可以与联吡啶盐结合的32-冠-10空腔,也包含有能与苄铵盐作用的24-冠-8空腔,并通过核磁验证了该四臂穴醚可以同时结合这两种客体。在此基础上,我们又进一步合成了等位的联吡啶客体和等位的二苄铵盐客体,并通过四臂穴醚与两种客体间的相互作用构筑了一种可进行酸碱调控的超分子聚合物。第三章,通过在穴醚的第三个臂上分别引入带有荧光的联萘酚基团和香豆素基团,我们成功的合成了两种基于32-冠-10冠醚的穴醚分子。这两种穴醚与联吡啶客体之间的主客体作用可以通过加入酸/碱进行调控,并且这两种穴醚与4,4-联吡啶的作用过程具荧光响应性,可用作酸碱调控的荧光分子开关。综上所述,本论文分别以冠醚和穴醚作为大环主体,进行了准轮烷型分子的构筑,并且初步探索了这些超分子材料的调控性能,对他们的刺激响应性和构象稳定性进行了研究,这些研究为后续进一步对基于这些大环主体的研究做出了探索和铺垫,并为基于类似的主体大环而构筑的分子识别与超分子智能材料提供了有益的参考与借鉴。更多还原

【Abstract】 As the basis of supramolecular chemistry,the macrocyclic molecular of generation after generation is found to be able to combine with guest molecular with special properties quickly and effectively.The supramolecular compounds are constructed by hydrogen bond,dipole-dipole,coordination,Fan Dehua force,π-π,and hydrophilicity hydrophobicity between the host molecular and the guest molecular.Pseudorotaxane and rotaxane are typical molecular machines constructed from the host and guest interaction,in which the chain guest can be included in the cavity of the macrocyclic molecular through intermolecular interaction.Rotaxane is developed from pseudorotaxane,but in rotaxane,both ends of the thread component there are introduced large stopper group to prevent the macrocyclic molecular from falling off the chain component.Through studying of the mechanism of host-guest interaction,the supramolecular has attracted more and more attention in life sciences and intelligent materials.Based on the classic crown ether and cryptand,we have constructed the supramolecular polymer and fluorescent molecule switch.In chapter 1,the development of supramolecular chemistry,application of crown ethers and cryptand are summarized.The molecular machines based on crown ethers and cryptand,the application of molecular machines in polymers,ion recognition and molecular switches are introduced.In chapter 2,in which BMP32C10 motif can bind with paraquat 2-2 while DB24C8 motif can bind with dibenzylammonium salt 2-3 in spite of the electrostatic repulsion between guests 2-2 and 2-3.On this basis,we further synthesized the allelic bipyridine guest 2-4 and the allelic dibenzylammonium guest 2-5,and ulteriorly we constructed a supramolecular polymer which could be regulated by acid and base.In chapter 3,the binaphthol group and coumarin group were introduced to the third arms of the BMP32C10.The host and guest interaction between the two cryptands and pyridine guests could be well regulated by adding acid/base,and the two cryptands and 4,4-bipyridine have fluorescence responsiveness,which could be used as fluorescent molecular switch regulated by acid/base.To sum up,the construction of pseudorotaxanes were carried out with crown ether and cryptand as macrocyclic host,and the regulatory property and stimulus responsiveness of these supramolecular materials were preliminarily explored,which provided useful reference for molecular recognition and supramolecular intelligent materials.更多还原