本論文為研究以吡啶衍生物做為軸配位基與鋅紫質螯合作用的光譜及電化學等性質研究。利用光度滴定法可測得吡啶與鋅紫質的形成常數(Kf0),研究顯示,吡啶分子之對位取代基的推、拉電子性,會影響吡啶的pKa,而影響形成常數數值的大小。 本論文之電化學研究結果顯示,以吡啶衍生物對ZnTMP進行滴定形成配位錯合物時,會使鋅紫質的第一個氧化往負電位的方向移動,表示失去一個電子之後的鋅紫質對軸配位基的親和力比其他氧化態的鋅紫質還高,而第二個氧化電位則往正電位的方向移動,表示比較難氧化。由電位的偏移量可以計算出各氧化態與吡啶衍螯合之形成常數。
In the thesis, a spectral and electrochemical study for zinc tetramesitylporphyrin (ZnTMP) in the presence of pyridines in CH2Cl2 solution were presented. A. Formation constants of ZnTMP / pyridines complexes wrer obtain by spectrophotometric titration. B. When ZnTMP form five-coordinated Zn(L)TMP with axial-ligand pyridines, the Soret and Q bands exhibit red-shifted in their obsorption spectra. C. Benesi-Hildbrand method was used to calculate the formation constants of oxidized species, ZnTMP+•and ZnTMP2+ with pyridines. Spectroelectrochemical method was used to obtain the absorption spectra of the complexed zinc porphyrin cation radicals and dications.