Study On Synthesis And Complexing Properties Of Calixarene Based Terpyridines

The terpyridine and its derivatives haveσ-electron-donor groups andπ-electron-acceptor groups. It can form the stable complexes with many kinds of metallic ions. It can be used as the model compounds of supramolecular devices such as molecule switch and molecule motor. Terpyridine metal complexes, not only have special structures, but also possess multiple properties such as electron transfer, energy transfer, irradiancy, electricity, magnetism and mechanical movement. Recently, the research and development of new kind of terpyridine and its derivatives are attracted much attention and have become one of most hot topics in supramolecular chemistry. The fusion of the terpyridine and calixarenes into a unique entity will give rise to new discovery in coordination chemistry and supramolecular chemistry. In this thesis we initiated the syntheses ofα,ω-dialkoxy-bridged bisterpyridines and calixarene based terpyridines, studies of preparation of polynuclear metallic complexes and their spectroscopic properties. The main achieved research results are as follows:1. Three series ofα,ω-dialkoxy-bridged bisterpyridines were efficiently prepared via the one-pot multicomponent reactions of 2, 2'- or 4,4'-dialkoxy-bridged and 3,3'-dimethoxy-4,4'-alkoxy-bridged benzaldehydes with 2-acetylpyridine and ammonia in alkaline conditions. The structures of the synthetic bisterpyridines were characterized with IR, 1H NMR, 13C NMR and HRMS spectroscopyas well as were further confirmed by determination of one representative single crystal structure.2. The condensation of 2-acetylpyridine and p-hydroxybenzaldehyde and ammonia in alkaline conditions yields key building block 4-hydroxyphenylterpyridine. Then it was alkylated with 1,2-dichloroethane, 1-chloro-3-bromopropane, 1-chloro-4-bromobutane to give the key intermediateω-chloroalkoxyphenylterpyridines. Finally alkylation of diffent kind of calixarene withω-chloroalkoxyphenylterpyridines in alkaline condition gave the novel one, two or four functional terpyridine subunits on calixarenes. The structures of all prepared compounds were characterized with IR, NMR spectroscopy and were further confirmed by X-ray diffraction determination of two representative single crystals. The synthesis, characterization and properties of calixarene-terpyridyl ruthenium complexes were systematically carried out.3. The compexing proepties of the six representative calixarene terpyridines for transition metal ions were studied with UV-vis and fluorescent spectroscopy. The compelxing constants and selectivity depending on the molecular structures were obtained.