Functional Modification And Application On Ion Recognition Of Calixarene

Calixarenes, the third generation supramolecular compound, are more liable to chemical modification. Many kinds of calixarene derivatives with versatile properties can be derived by modifying the up-rim and the down-rim of the calixarenes. With special physical and chemical properties, they have been found versatile applications in number of research fields including molecular recognition, self-assembly, nano materials and catalyst, so it has been attracted greet interests in home and abroad. Calixarenes modified by heteroatom-containing groups have good complexation and recognization abilities towards heavy metal and transitional metal cations, thus can be widely used in various fields. In this thesis we have synsized a series of calixarene derivatives containing nitrogen and oxygen atoms, then we also have studied the complexing properties of the prepared functional molecules for transition metal ions . Some meaningful results were obtained.1. Under the catalysis of concentrated hydrochloric acid, 3-methoxyphenol was reacted with aldehyde to form tetramethoxyresorcinarene. The tetrame thoxyres- orcinarene was alkylated with N-3-bromopropyl and N-4–bromrobutulphthimide to give tetrasubstituted derivatives. Then with reactions of hydrazinolysis, condensation with salicylaldehyde, 2-pyridinecarboaldehyde sucessefully, a series of calixarene schiff bases were obtained. Their structures were characterized by NMR and IR.2. Tetramethoxyresorcinarene and resorcinarenes can be efficiently alkylated with chloroacetate to give activated ester derivatives, which in turn were ammonolyzed with hydrazine or diamines to give hydrazone and amide derivatives. Then the schiff bases could be prepared by the condensated of above hydrazone and amide derivatives with salicylaldehyde and 2-pyridinecarboaldehyde. Besides characterizing their structures by NMR and IR, six single crystal structures were determined by X-ray diffraction method.3. The compexing proepties of the tetramethoyresorcinarene and resorcinarenes schiff bases for transition metal ions were studied with UV-vis spectroscopy, from which we could obtain the association ratio of the hosts with Cu2+ and Zn2+. Then the association constants of the coordination complex also could be caculated. The results turned that schiff bases had distinct selectivities for transition and heavy metal ions, specially for Zn2+,Cu2+,Hg2+,Co2+,Ni2+.