Spectral and electrochemical characterization of new vanadyl ,copper and zinc porphyrins

• Main Authors: Chiu, Hsien-Ju, 邱顯儒
• Other Authors: Su,Yuhlong Oliver
• Format: Others
• Language: zh-TW
• Published: 2002
• Online Access: http://ndltd.ncl.edu.tw/handle/62931549030355050125

碩士 === 國立臺灣大學 === 化學研究所 === 90 === Abstract We reported synthesis of nonaqueous porphyrins about ZnENP, CuENP with naphthoic ester and ZnHNP, cis-VOHNP and trans-VOHNP with naphthoic acid. The electrochemical properties of porphyrin have been studied by cyclic voltammetry (CV) and spectroelectrochemistry. There are two reversible redox couples in the CV of ZnTMP and ZnENP at oxidation potential. Observation by UV-vis-near IR spectroelectrochemistry indicated that ZnENP was first oxidation to cation radical ,ZnENP+· and that the second oxidation renders rapid intramolecular chemical reaction to form isoporphyrin. ZnHNP was first oxidation renders rapid intramolecular chemical reaction to form isoporphyrin. The electrochemical properties of CuENP is similar to ZnENP. The electrochemical properties of CuHNP, cis-VOHNP and trans-VOHNP are similar to ZnHNP. VOHNP has two isomers in the forms of cis-form and trans-form. VOTMP, cis-VOHNP and trans-VOHNP are titrated with 6 kinds of monodentate ligands and 4 kinds of bidentate ligands under UV-vis spectra detection. There is axial ligand selectivity when trans-VOHNP is titrated with pyridine and ethylenediamine. In the case of pyridine, it can not be ligated with trans-VOHNP and there is no change on UV-Vis spectra. In the case of ethylenediamine, the formation constant of trans-VOHNP is three order larger than those of VOTMP and cis-VOHNP.