Design,Synthesis And Properties Of Novel Nitrogen-containing Macrocycles

Macrocycle refers to an organic compound with a cyclic structure connect by 12 or more atoms.It can participate in the recognition and assembly process through a variety of non-covalent interactions.Therefore,macrocycles play an extremely important role in the development of supramolecular chemistry.Since the establishment of supramolecular chemistry,there are plentiful macrocycles such as crown ether,calixarene,pillararene,cucurbituril and so on being reported,which have promoted the rapid development of supramolecular chemistry.Various materials based on macrocycles have been widely used in the fields of chemistry,biology,materials science,and so on.Due to abundant source,easy functional modification,and good photoelectric properties,nitrogen-containing arenes have been used in the synthesis of macrocycles.The introduction of nitrogen atoms in macrocycles not only enrichs macrocycles but also make them fine host-guest properties.In the meantime,functional materials based on nitrogen-containing macrocycles exhibit excellent properties,which has attracted widespread attention.Based on abovementioned points,this thesis systematically studied the properties of methylene bridged and conjugated nitrogen-containing macrocycles in host-guest recognition,assembly,and radical properties.This thesis mainly includes the following five parts:In Chapter one,the outstanding contribution of macrocycles in the establishment and development of supramolecular chemistry is first introduced,which can clarify the importance of macrocycles.Then,the macrocycles synthesized by Friedel-Crafts alkylation reaction and Yamamoto coupling reaction as well as their applications are summarized.Finally,the research progress of nitrogen-containing macrocycles is summarized.In Chapter two,diphenylamine and its derivatives have been used for synthesis of one kind of new methylene-linked nitrogen-containing macrocycle DPA[n](n=3-7),followed by the investigation on the structure,assembly,and host-guest interaction.Due to the unique structure of diphenylamine,DPA[3]and DPA[4]have the ability to assemble throughπ-πinteractions,which are systematically studied through nuclear magnetic resonance,dynamic light scattering(DLS),diffusion ordered spectroscopy(DOSY),atomic force microscopy(AFM)and scanning Electron microscopy(SEM).Finally,gas adsorption and X-ray single crystal diffraction proved that DPA[3]has the ability to complex with ethene and ethyne.Meanwhile,the first single crystals of host-guest complexes composed of macrocycle and ethene or ethyne have been obtained.In Chapter three,keep the unstable of nitroxide radicals formed by diphenylamine in mind,one diphenylamine macrocycle DPA[3]-NO containing stable nitroxide radical was synthesized through the assembly of diphenylamine macrocycle.The assembly of the macrocycle was studied through DLS,transmission electron microscopy(TEM)as well as coarse-grained molecular dynamics simulations.Finally,the macrocycle can be used for the oxidation of alcohol compounds,and exhibited more excellent catalytic performance than TEMPO due to the high stability and less steric hindrance of the nitroxide radical on the macrocycle.In Chapter four,the first aryl-substituted conjugated carbazole macrocycle M_n(n=5-7)was synthesized followed by the investigation on radical and host-guest properties.Due to the introduction of the aryl group to the macrocycles,which could increase the solubility of the macrocycles,large-sized conjugated carbazole macrocycles have been synthesized.In the meantime,the aryl group reduces the oxidation potential of the carbazole and improves the stability of the carbazole radical cations,and the first stable carbazole-based radical cation was obtained,which was systematically studied by CV,UV-vis-NIR,EPR,single crystal X-ray diffraction as well as computational simulation.In the end,the host-guest interaction between the pentamer macrocycle and the fullerene molecules was investigated through NMR,Job plot,mass spectrometry and computational simulation.In Chapter five,an aryl-substituted methylene-linked phenothiazine macrocycle CPT[n](n=3-4)was synthesized followed by the investigation on radical,host-guest properties of this new macrocycle together with its application.The introduction of the aryl group increases the stability of the phenothiazine macrocycle-based cation radical.In consequence,CPT[3]and CPT[4]can be oxidized to stable radical cation species,which were systematically studied through CV,UV-vis-NIR,EPR and computational simulation.Due to the excellent redox properties of CPT[3]and CPT[4]as well as the high stability of phenothiazine macrocycle-based radical cations,CPT[3]and CPT[4]show exhibits stability and coulombic efficiency when they were used in organic battery materials.