臺灣博碩士論文加值系統

本論文在紫質環meso-位置上置換phenyl, mesityl, 2,6-dichlorophenyl 和 triphenylamine (TPA)的取代基，合成一系列對稱的紫質與鐵紫質。利用循環伏安法與光譜方法觀察這些物質的氧化還原電位與光譜性質，並且發現這些物質的形式電位符合推拉電子效應； FeTDPAPP(Cl)因為三苯胺與紫質環的作用，所以UV-Vis吸收峰比較寬大並且有紅移的現象。並且我們利用TBAOH滴定鐵紫質，以光譜與電化學方法觀察鐵紫質配位過程的變化。
由文獻上我們得知鐵紫質單體在溶液狀態下具有良好的催化活性，並且已經被廣泛研究，於是我們研究三苯胺鐵紫質的電化學性質並研究製備成修飾電極的可能性。我們發現含三苯胺的鐵紫質具有電聚合的能力，並且可以修飾在電極表面上；而另外三種沒有電聚合能力的鐵紫質，可以利用EDOT電聚合成PEDOT時，將鐵紫質摻入到膜中。並且以電化學、EQCM、UV-Vis和SEM等方法觀察到修飾薄膜的性質。

A series of symmetric porphyrin rings bearing phenyl, mesityl, 2,6-dichlorophenyl and triphenylamine (TPA) pendant groups and their iron complexes were synthesized. Cyclic voltammetry and spectral methods were used to examine the redox potentials and optical properties of these compounds. The formal electrode potentials of iron porphyrins are in agreement with the electron-donating-withdrawing properties of the substituents on the phenyl groups. The B and Q bands of FeTDPAPP(Cl) are located at higher wavelengths and the bandwidths become broader compared with those of the other porphyrins, indicating the peripheral TPA affects the electronic configuration of iron porphyrins. Titration of iron porphyrins with tetra-n-butylammonium hydroxide (TBAOH) as the axial ligands was monitored by spectrophotometry and cyclic voltammetry.
The preparation method and characterization of iron porphyrin modified electrode was also studied. It was observed that FeTDPAPP(Cl) monomer can be electropolymerized and incorporated onto the electrode surfaces. The other three iron porphyrins can be used as dopant molecules when electropolymerable monomer (EDOT) was co-existed as mixtures. The polymeric films were characterized by electrochemical and spectral measurements.

謝誌..........................................................Ⅰ
摘要..........................................................Ⅲ
Abstract......................................................Ⅳ
目錄..........................................................Ⅴ
圖目錄........................................................ⅤⅡ
表目錄........................................................ⅩⅡ
第一節 緒論 1
1.1 紫質 (porphyrins) 與金屬紫質 (metalloporphyrins) 1
1.2 含三苯胺取代基的紫質 3
1.3 PEDOT (poly-3,4-ethylenedioxythiophene) 8
1.4 化學修飾電極 (chemically modified electrodes) 9
1.5 研究目的 16
第二節 實驗部份 19
2.1 藥品 19
2.2 儀器 19
2.3 實驗準備 22
2.4 合成 24
2.5 吸收係數的測量 37
2.6 形成常數的測定 53
第三節 結果與討論 64
3.1 UV-Vis光譜研究 64
3.1.1 porphyrins free base與iron porphyrins的光譜性質 64
3.1.2 TBAOH滴定Iron porphyrin的光譜研究 67
3.2 電化學性質研究 68
3.2.1 Porphyrin free bases 68
3.2.2 Iron porphyrins 77
3.2.3 Electrochemistry of iron porphyrins in the presence of OH-89
3.3 電極修飾薄膜的研究 95
3.3.1 poly-FeTDPAPP(Cl)電聚合膜鑑定與性質探討 95
3.3.2 FeTPP(Cl) doped film的研究 106
第四節 結論 116
參考文獻 117

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