二茂铁衍生物现场红外光谱电化学以及导数循环伏吸法的分析-分析化学专业论文.docxVIP

Abstract In this report, experimental technique, application and development of in-situ FTIR spectroelectrochemistry (FTIRs), derivative cyclic voltabsorptometry was introduced firstly. Secondly, A series of ferrocenyl complexes: 1,4-bis(2-ferrocenyl- vinyl)benzene, 2 – ferrocenylfuran (FcF) and 2, 5 – diferrocenylfuran (Fc2F) were designed, synthesized and characterized. A systematic investigation of the electron transfer (ET) behavior of the ferrocenyl derivatives was undertaken. At last derivative cyclic voltabsorptometry on ferrocenyl complexes provide new useful information that electrochemistry or in-situ FTIRs single cannot give. A series of ferrocenyl derivatives were designed. 1,4-bis(2-ferrocenylvinyl)- benzene was synthesized by Wittig reaction. FcF, Fc2F were synthesized by cross-coupling reaction of bis(ferrocenyl)mercury (Fc2Hg) with aryl iodides. Then, IR, MS and 1H-NMR were used to character these complexes. Electron transfer mechanisms and electron pass pathways of these ferrocenyl derivatives were studied by cyclic voltammetry (CV), differential pulse voltammetry (DPV). The results show that 1,4-bis(2-ferrocenylvinyl)benzene seemed to undergo a one consecutive two-electron step and the potential value of FcF was considerably more positive than that of ferrocene at the same experiment conditions, this is due to the strong electron withdrawing effect of the furan substituent which binds directly to the cyclopentadienyl ring, making oxidation of the ferrocene unit more difficult than that of unsubstituted metallocenes; Fc2F was compared with the analogous derivative1,4-(diferrocenyl)benzene, the oxidation potential of 1,4-(diferrocenyl)- benzene had slightly negative shift, indicating that the electron density in the ferrocene increased because of the benzene ring compared with Fc2F. In-situ rapid scan FTIR and In-situ difference FTIR Spectroelectrochemistry technique were used to track the whole electrochemical redox process of the complexes as var