| Summary: | 博士 === 國立暨南國際大學 === 應用化學系 === 97 === The thesis involves two parts. The first one includes the synthesis, electrochemical and spectral studies of phenylenediames and oligoarylamine. 4,4’-Azo-bis(triarylamine) derivatives with electron-donating groups have been synthesized. Their spectral and electrochemical characteristics have been investigated. Their first and second oxidations exhibited different degree of overlapping, depending on the electron-donating groups at the para-position of the phenyl rings. The stability of the oxidation products was monitored with UV/VIS/NIR spectroelectrochemical methods. The derivatives have very stronger IV-CT band in the near-IR range.
Hexamer has been synthesized and the electrochemical and spectral porperties also have been investigated。In the electrochemical study, haxamer has totally four-electron transfer in the oxidation. With the smaller of electrolyte anion, the oxidation potetial shifted anodically. The spectral change of the hexamer in different oxidation states were similar to that of TPPD.
In the second part, metalloporphyrins with azobenzene substituents have been synthesized and their electrochemical properties have been investigated. The derivatives exhibit unusual spectral and electrochemical properties. The porphyrin ring as well as azobenzene substituents could be reduced. The reduction potential varies with solvent and axial ligand. Spectroelectrochemical method is used to monitor the spectral change of the metalloporphyrins at different potential. EPR results for oxidized zinc porphyrins indicate that the radicals are localized in the porphyrin ring.
ZnTMP-PD was synthesized and fully characterized. By using electrochemical and spectroelectrochemical method, ligand shuttling between zinc porphyrin and meso-phenylenediamine substituent could be monitored. EPR results indicated that charge would delocalize on ZnTMP-PD.
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