Study On Synthesis, Properties And Applications Of Novel Ferrocenyl Compounds Containing Amide And Ester Group

Ferrocenyl anion receptors have been proved to be one of the most effective anion sensing materials. The study of design and synthesis of ferrocenyl anion receptors has become a a burgeoning field of study in the last twenty-five years. In this thesis, we focused on the synthesis of ferrocenyl anion receptors with multi-signalings, dendrimers and hyperbranched modified by ferrocene and ferrocene-substituted poly(phosphazene), in view of their preparations, properties and applications.(1) A novel Schiff base based ferrocenyl compound 5-nitrosalicylaldehyde-ferrocenylhydrazone (FcSA-2) in which the ferrocene unit was connected with a nitrophenol has been designed and prepared via a very simple way. The electrochemical behaviors of FcSA-2 in different ratios of DMSO/CH2Cl2 mixture were investigated and FcSA-2 showed a "solvent recognition" behavior with the increase of DMSO percent in mixture. DMSO was utilized as not only a solvent, but also a "binding valve" in the electrochemical sensing of anions for the first time. FcSA-2 showed high selectivity for F-with both electrochemical and optical responses in DMSO. The anion recognition was valuated by electrochemistry, UV-vis and 1H NMR. It is found for the first time that the amide N-H participated in the formation of intramolecular ring instead of the anion binding event. The preferred binding mode of FcSA-2 and F-was proposed for the most representative complex by means of density functional theory (DFT) based on theoretical calculations and also confirmed the existence of a seven-membered intramolecular ring formed by the hydrogen-bonding interaction of amide N-H and keto after deprotonation of O-H by F-.(2) A very simple fluoride ion receptor FcSA was synthesized and it showed fluorescence "switch on" by combining suppression of C=N isomerization with deprotonation of fluoride ion. FcSA can selectively sense the fluoride in DMSO through three channels i. e. redox shift, color change and fluorescence "switch on" which make the sensing process more convincing. Plus, the redox shift can be changed into fluorescence "switch on" in our system by varying the amount of fluoride ions, on the basis of which we may design a ternary logic gate. Moreover, the DMSO acts not only as solvent, but also a "binding valve" in the electrochemical sensing of anions for the first time. The role of DMSO that played in this work implied that we may take the advantage of the solvent in the binding event instead of avoiding the effects of the solvent.(3) A kind of dendrimer (Dend-Fc-OH) with heterochains comprised by ferrocenyl groups and hydroxyl groups, two kinds of ferrocene modified hyperbranched polymers (HP-Fc-1 and HP-Fc-2) were synthesized. Electrochemical behaviors of Dend-Fc-OH, HP-Fc-1 and HP-Fc-2 were investigated by CV and influences of solvents and scan rate on the electrochemical behaviors of Dend-Fc-OH, HP-Fc-1 and HP-Fc-2 were discussed. Anion recognition abilities of Dend-Fc-OH, HP-Fc-1 and HP-Fc-2 were studied by CV and their binding models with anions were proposed.(4) A novel kind of ferrocene substituted poly(phosphazene) was synthesized. The amide on the side chain was able to act as the anion binding site and the ferrocene group can be used as the electrochemical signaling unit. Electrochemical behaviors of Fc-L and PN-Fc were investigated by CV and influences of solvents on the electrochemical behaviors of Fc-L were discussed. The anion recognition of Fc-L and PN-Fc in CH2Cl2 were investigated by CV. The order of anion recognition of Fc-L was H2PO4-> F-> I-> Br-> HSO4-> C1-> NO3-. Compared with Fc-L, the recognition ability of PN-Fc towards HSO4- was largely. It is possible that the bidentate structure formed by two ferrocenyl chains on one phosphorus atom was able to bind the HSO4-strongly.