Synthesis and Electrochemical Studies of Porphyrins Substituted with Two Triphenylamines

[[abstract]]本論文主要是探討具對稱meso-三苯胺取代基紫質的合成與電化學性質。將具對稱meso-三苯胺取代基紫質加入鋅離子成為鋅紫質，用滴定咪唑(N-methyl imidazole)的方式，形成配位的鋅紫質，使用循環伏安法可觀察到紫質環的氧化電位改變，再使用透光薄層電化學法(optically transparent thin-layer electrode，OTTLE)觀察紫質經過氧化後的光譜，因此，可以判斷紫質環與三苯胺氧化的先後順序。 無金屬的對稱meso-三苯胺取代基紫質可由OTTLE與比較對稱meso-三苯胺取代基鋅紫質的電位，判斷紫質環與三苯胺氧化的先後順序。實驗的結果顯示，對稱meso-三苯胺取代基鋅紫質因三苯胺上推拉電子基強弱的不同，會使三苯胺的中心氮的氧化有所影響，大部分都是紫質環先氧化。[[abstract]]We have synthesized a series of symmetric zinc porphyrins and porphyrin free bases with triarylamine substituents. Cyclic voltammetry and spectroelectrochemistry were used to monitor the changes of redox potential and absorption spectra of those compounds. Besides, the substituent effect to the central metal porphyrins and porphyrin free bases was investigated. By use of titration method in cyclic voltammetry, imidazole coordination to zinc porphyrins could cause the potential shift in oxidation. In spectroelectrochemistry, TPA or porphyrin rings as oxidation sites could be distinguished by setting the potential stepwise.[[note]]碩