Synthesis And Property Study Of Oxacalix [4] Arenes And Azacalix [2] Arene [2] Carbazoles

Calixarenes are considered as a new generation of host molecules due to theirsynthetic availability, high level of pre-organization and versatile molecularrecognition properties. In recent years, heterocalixarenes, in which the methylenelinkages between the aromatic units are replaced by hetero-atoms such as oxygen,nitrogen, sulphur, phosphorus, silicon and tin have gradually attracted molecularscientists’ interests. The introduction of heteroatoms has resulted in diverseconformations and molecular recognition properties of this class of host molecules,especially oxacalix[4]arenes and azacalix[4]arenes. This thesis will highlight ourresearches on the synthesis and property study of novel oxacalix[4]arenes andazacalix[2]arene[2]carbazoles.Except for a few cases, most reports about derivations were focused mainly onthe introduction of functional groups before oxacalix[4]arene skeleton formed. In partone of this thesis, we successfully design a route to synthesize highly functionalizedoxacalix[4]arene and then do further post-macrocyclization functionalization withhigh efficiency. This route is flexible enough to enrich the derivation andfunctionalization of oxacalix[4]arenes. Because oxacalix[4]arene usually adopts a1,3-alternate conformation, we choose it as scaffold for the constructionsupramolecular polymer upon introduction of four hydrazide motifs as hydrogenbonding building blocks. Monomers are linked by four hydrogen bonds at each knotand the association strength is strong enough to ensure the formation of double-arraysupramolecular polymer in solution.Carbazole is a highly photoelectric molecule. The direct incorporation of acarbazole subunit within the macrocyclic framework has important influence on theexploration of new materials. In part two of this thesis, we design two routes tosynthesize azacalix[2]arene[2]carbazoles which incorporates carbazoles within theframework. One strategy towards a2+2product is through a one-step nucleophilicaromatic substitution synthesis, and has good yield. In order to establish a differentmethod for the synthesis of non-symmetric azacalix[2]arene[2]carbazoles, we also explore a stepwise fragment coupling approach. We firstly synthesize differentfragment molecules through controlling the reactants ratio, then we get the3+1product via fragment coupling. Different groups can be introduced into theazacalix[2]carbazole[2]arenes via this method, which will make the structures andproperties more diverse.