Synthesis, Derivatization And Nonporous Adaptive Crystals Property Study Of Hexnutarenes

Supramolecular chemistry plays an important role in the field of chemistry,and macrocyclic chemistry is a vital important part of supramolecular chemistry.The syntheses,derivatives and properties of new macrocycles have been central research topics in macrocyclic chemistry.In recent years,a variety of new types of macrocyclic arenes have emerged,such as Tiara[5]arene,Leaning pillar[6]arene and Terphen[n]arenes.The common structure feature of these macrocyclic arenes is that the monomers(fragments)act as repeating units linked by methylene groups to form cyclic molecules.After synthesizing these new macrocycles,not only the host-guest properties were studied,but also the macrocycles were prepared into nonporous adaptive crystals(NACs)to study the properties.The research work of this thesis mainly focused on the novel macrocyclic arenes syntheses,derivatives,the preparation of NACs and performance studies.In the chapter 1,Suzuki coupling reaction,the syntheses of various macrocyclic arenes and their research progress were introduced.And then,the use of macrocyclic arene NACs were introduced.In the chapter 2,a biphenyl fragment which was para-linked by methylene bridge was synthesized with the Suzuki-Miyaura reaction.Then in the system of methylal and boron trifluoride ether,the macrocyclic arene of 12 fully para-linked aromatic rings was synthesized with the biphenyl fragment by a one-pot reaction.This macrocycle was named after its shape as hexnut[12]arene.The method is simple and easy to operate,and the yield is satisfactory(up to 40%).In this chapter,it is the first time to introduce methylal as a carbon source for macrocyclic arene methylene bridges instead of paraformaldehyde.It enriches the methods of fragments polymerizing into macrocycles.And the mechanism of fragment polymerization macrocycles was also explored.The structure of HN[12] was further confirmed by the single X-ray diffraction characterization.Finally,a water-soluble HN[12] was synthesized and host-guest properties were explored with paraquat derivative in water.In summary,in this chapter,A new method for the synthesis of novel macrocycles has been developed.And this method solved the current problem of low yields in the synthesis of macrocyclic arenes with more than full 10 para-linked aromatic rings(e.g.2% for pillar[10]arene).And host-guest properties of macrocyclic arenes were explored.In the chapter 3,in order to further study the generality and reliability of the synthetic methods,the effects of solvent types,catalyst types and temperature were explored by using sulfur-bridged fragment as an example.Then optimal conditions for the polymerisation were obtained.Subsequently,various fragments including heteroatomic bridge and aryl bridge were synthesized by the Suzuki-Miyaura reaction.Finally,under optimal conditions,the polymerisation of the fragments into hexnutarene was achieved.By polymerising various fragments into hexnutarenes,not only it demonstrated that V-shaped fragments with appropriate angles were beneficial to formation of hexnutarenes,but it also demonstrated the prevalence and stability of macrocyclic formation by polymerisation of methylal and boron trifluoride ether systems.The traditional derivation strategy of the macrocycle on the methylene bridge is basically to form the macrocycle before derivation.Derivative methods were demanding.However,hexnutarenes were first derived on the methylene bridge and then polymerized into macrocycles.The derivative strategy was simple and effective.Finally,the photophysical properties of hexnutarenes and their derivatives are also explored.In this chapter,the methods of macrocyclic synthesis were validated and enriched the concept of macrocyclic design by derivatization of hexnutarenes.Chapter 4 focused on the properties of hexnutarenes NACs.The conditions for the preparation of HN[12] NACs were explored.HN[12] NACs of single crystal and crystal powder were prepared to study the adsorption performance of iodine and basic fuchsine.The kinetic process of adsorption was also investigated.Comparing the results of NACs adsorption of single crystal and crystalline powder,it is found that the adsorption performance of NACs prepared from crystalline powder is better than that of single crystals.In this chapter,we mainly investigated the adsorption of HN[12]NACs.In addition,the stability of the NACs performance was also investigated by HN[12] NACs adsorption cycling experiments.Finally,the adsorption of commonly used industrial gases by hexnutarenes and their derivatives is explored.The purpose is to provide an important reference for the subsequent use of hexnutarenes for adsorption and separation.Chapter 5 was the conclusion and outlook.