Synthesis, Structure and Characterization of Hexaazamacrocyclophane Europium, Gadolinium and Vanadyl Complexes

• Main Authors: Chao-Min Yang, 楊釗旻
• Other Authors: Wen-Jwu Wang
• Format: Others
• Language: zh-TW
• Published: 2004
• Online Access: http://ndltd.ncl.edu.tw/handle/88114481749380085812

碩士 === 淡江大學 === 化學學系 === 92 === A novel method to prepare macrocyclic compound of hexaazacyclophane, H2HAPP, and its metal derivatives was developed and reported in our laboratory. These compounds, analog of porphyrins and phthalocyanines, have unique chemical and physical properties. Recently, transition metal complexes of porphyrin and phthalocyanine with decker-shaped structure were reported. In this presentation, mono-decker complexes with H2HAPP ligand were reported. Initially, transition or inner transition metal acetylacetonates and H2HAPP was dissolved in 1,2-dichlorobenzene (ODCB) or 1,2,4-trichlorobenzene (TCB) with high temperature in refluxing over 11 hours. The mono H2HAPP- decker complexes were obtained in such situation of reaction. Product will mix with impurities in solvent and it isn’t easy to remove solvent in vacuum. Finally, rare earth metal acetylacetonates and H2HAPP were dissolved in methanol in refluxing. To remove all liquid in the reactor in vacuum. We just repeated the two steps again and again and gained product in high yield and degree of purity. Phenol will instead of methanol in reaction of vanadyl macrocycle complex without vacuum. Within methanol solution, they exhibited axial ligand exchange effect and aggregation effect. We didn’t gain any X-ray diffraction data, but other indirect spectroscopy and analysis showed the rationalities. For a certainty, rare earth metal and transition metal H2HAPP complexes both had lots of different characterizations. Even now several properties never showed in porphyrins or phthalocyanines complexes within the same metals.