Study On The Synthesis Of Calix[4]arene Nitrogen-containing Functionalized Derivatives And Metal Complexes

Calixarenes are known as the third generation supramolecular host compounds after crown ethers and cyclodextrins. Due to its chemical stability, high melting point and adjustable cavity, much attention are payed to synthesis and applications of calixarenes. Recently the ability of coordination and recognition of ions and molecules has been greatly enhanced by introducing various functionalized groups to the upper rim or the lower rim of the calixarenes. Schiff base’s compounds and their metal complexes have important applications in the field of medicine, catalysis and analytical chemistry because of the synthetic convenience and chemical stability of the Schiff bases. It seems that the study of calixarene-based Schiff bases and their metal complexes has been investigated in some details. In this thesis, we wish to use calix[4]arene as the platform to prepare a series of nitrogen-containing functionalized derivatives, and their transition metal complexes. Some interesting research results are as follows:1. Some new kinds of the functionalized terpyridines bridging N-imidazolium salts, thiacalixarenes and cyclotriveratrylenes were succefussfully prepared by alkylation of4’-substituted2.2’:6’,2"-terpyridine and subsquential addition reaction. These functionalized terpyridines could chealted transition metal ions. The structures of them are characterized by IR. NMR spectroscopy and X-ray diffraction method.2. A series of large macrocyclic calixarene bishydrazones were efficiently synthesized by [2+2] condensation reactions of calix[4]arene1,3-disubstituted aldehydes with hydrated hydrazine or butanedioyl hydrazine. The structures are characterized by IR spectroscopy, NMR and were further confirmed by X-ray diffraction determination of four representative single crystals, which showed that macrocycles form a distinctive calixtube-liking shape.3. A series of calixarene Schiff base polydentate ligands were obtained by the condensation of calix[4]arene1,3-disubstituted aldehydes with some acyl hydrazides. The coordination properties of these ligands with transition metal ions were studied. One single crystal structure of transition metal complex were successfully determined by X-ray diffraction method. This complex was formed a large macrocyclic structure with two metal ions as cyclic number.