Synthesis And Property Of Several Heteracalix[4]aromatics And Watersoluble Corona[n]arenes

Macrocycles provide powerful tools in the study of non-covalent interactions because of their unique pre-organized structures.The development of new functional macrocycles promotes the advances of both supramolecular chemistry and organic chemistry.Macrocycles play important role in molecular recognition and assembly as well as in the research of organic reactions and mechanism study.This dissertation focuses on the synthesis,structures and properties of several functional heteracalix[4]aromatics and coronarenes.The macrocyclic monoaryl-Ni(II)complexes were synthesized efficiently by the interactions of azacalix[m]arene[n]pyridine(m = 1,n = 3;m = 2,n = 2)and nickel(II)salts via aryl C-H activation.The more stable diaryl-Ni(II)complex was also obtained in good yield.Both complexes were fully characterized.The transformation of aryl C-Ni(II)bond to C-C bond,C-O bond,C-N bond,C-Br bond was achieved.More interestingly,we found that the azacalix[1]arene[3]pyridine-Ni(II)complex reacts with both nucleophiles and electrophiles,while azacalix[2]arene[2]pyridine-Ni(II)complex is inactive with these reactants under various conditions.Three kinds of inherently chiral heteracalix[4]aromatics were synthesized and they include azacalix[2]nitrobenzene[2]pyridines,heteracailix[2]naphthalene[2]pyridines and heteracalix[2]arene[2]isoquinolines.Two pairs of enantiomers were resolved using chiral HPLC method and their CD spectrum were measured to confirm the exist of enantiomers.The interactions between oxygen bridged calix[2]perfluoroarene[2]triazines and several anions based on anion-pi interaction were re-examined.It was found that the macrocycles were not stable in the presence of nucleophilic anions such as azide,fluoride,acetate anion,cyanogen anion.Other anions including tetrafluoroborate were also studied but host-guest interactions do not result in the spectrum variation.Two S6-corona[3]arene[3]pyridazines with electron-rich hydrophobic cavity were synthesized.Interactions between these two host molecules with cations of different charges and structures were studied by means of NMR,UV-Vis titrations and isothermal titration calorimetry(ITC)experiment.Host-guest interactions leads to the formation of 1:1 complexes,with the binding constants up to(3.15±0.35)×106 M-1.The binding strength was effected by the number of charges,volumes and structures of both hosts and guests.In summary,the study of the synthesis,structures and properties of several heteracalixaromatics and corona[n]arenes has demonstrated that both macrocyclic host molecules are useful and have promising applications in both supramolecular chemistry and organic chemistry.We believe that the development of novel and functional macrocycles would promote the better advances of supramolecular chemistry.