- 學位論文
具三苯胺三取代紫質的合成，電化學以及光譜電化學研究
Synthesis and Electrochemical Studies of Porphyrins Substituted with Three Triphenylamines
摘要
本論文主要是探討三苯胺三取代紫質的合成與電化學性質。合成的三苯胺三取代鋅紫質以循環伏安法實驗，配合滴定N-methylimidazole形成五配位的軸配位鋅紫質的方式，觀察鋅紫質的紫質氧化電位移動較三苯胺氧化電位移動明顯，以判定循環伏安法各個氧化屬於紫質或是三苯胺；再使用透光薄層電化學法(optically transparent thin-layer electrode，OTTLE)觀察紫質氧化後的光譜，循環伏安法與OTTLE實驗結果相互驗證，可以判斷紫質環與三苯胺氧化的先後順序。無中心金屬的三苯胺三取代紫質由循環伏安法與OTTLE，判斷紫質環與三苯胺氧化的先後順序。 實驗的結果顯示，三苯胺三取代鋅紫質第一個氧化為紫質環氧化，第二個氧化為三苯胺的氧化，且三苯胺上推拉電子基強弱的不同，於CV顯示取代基效應。UV/Vis吸收光譜研究結果亦證明三苯胺取代對於三苯胺三取代取代鋅紫質的取代基效應。而無金屬三苯胺三取代紫質，隨著三苯胺上推拉電子基的不同，而從不同部份開始氧化，-OCH3取代的三苯胺三取代紫質從三苯胺中心氮開始氧化，-NO2取代的三苯胺三取代紫質則是從紫質環開始氧化，-CH3以及-H取代的三苯胺三取代紫質則是三苯胺中心氮以及紫質環同時氧化。
並列摘要
Triphenylamine tri-substituted zinc porphyrin and their free bases were synthesized. From cyclic voltammetry studies, five coordinated zinc porphyrins could be obtained when the presence of N-methylimidazole, and it cause the oxidative potential of zinc porphyrins shifts. Spectroelectrochemical methods(optically transparent thin-layer electrode，OTTLE) were used to monitor the changes of absorption spectra of the zinc porphyrins and porphyrin free bases when potentials were applied. Cyclic voltammetry and OTTLE can estimate for the priority of oxidation potentials between the poyphyrin ring and the triphenylamine substitutent. In electrochemical, spectroelectrochemical, and UV/Vis absorption spectra studies, we observed the substitutuent effect of the triphenylamine-subtitutent of the porphyrins. In zinc porphyrins, the potential of the porphyrin ring cation radical is more negative than the potential of the triphenylamine cation radical. But it is opposite to porphyrin free bases, the potentials of triphenylamine cation radical and the potentials of porphyrin ring cation radical depend on the triphenylamine substitutent.