臺灣博碩士論文加值系統

本論文主要是合成具有三苯胺單取代基之紫質、鋅紫質和鈷紫質，H2M(TPA)TPP、ZnM(TPA)TPP、Co(II)M(TPA)TPP，且探討其光譜性質和電化學性質。在UV-vis吸收光譜上，其B band的莫耳吸收係數比相對應之H2TPP、ZnTPP、Co(II)TPP小且吸收峰變得比較寬。在電化學性質方面，因為受到三苯胺單取代基推電子的能力影響，使得紫質環變得容易氧化且不易還原。最後探討具有四個三苯胺取代基紫質、鋅紫質、鈷紫質(H2TDPAPP、ZnTDPAPP、Co(II)TDPAPP)，和具有三苯胺單取代基之紫質、鋅紫質和鈷紫質的光譜性質和電化學性質的不同。具有四個三苯胺取代基紫質的吸收峰和氧化電位改變等電化學跟光譜特性，都比三苯胺單取代基之紫質還要來得顯著。推測是因為紫質的電化學特性和光譜特性，會受到接上三苯胺取代基數目不同而改變。

In this study, the spectral properties and electrochemistry of porphyrin free bases、zinc porphyrins and their cobalt porphyrins bound with mono triphenylamine unit are investigated. Absorption spectral study indicates that the molar extinction coefficients and bandwidths of B band of H2M(TPA)TPP (meso-mono(triphenylamine)triphenyl -porphyrin)、ZnM(TPA)TPP (meso-mono(triphenylamine)triphenylporphinatozinc) and Co(II)M(TPA)TPP (meso-mono(triphenylamine)triphenylporphinatocobalt) are lower and broader than those of H2TPP(meso-tetraphenylporphyrin)、ZnTPP (meso-tetraphenylporphyrinato -zinc) and Co(II)TPP (meso-tetraphenylporphyrinatocobalt). Electrochemical study indicates that the strong electron-donating properties of TPA groups affect the porphyrin rings, which are easier to be oxidized and harder to be reduced. Finally, the properties of porphyrins bound with mono- and tetra-triphenylamine units are compared in their UV/Vis spectra and electrochemistry. Electrochemical half-wave potentials and B band bandwidth of porphyrins bound with tetra-triphenylamine units are smaller and broader than that of porphyrins bound with mono triphenylamine unit. It is proposed that the spectral properties and electrochemistry of porphyrins are related to relations with the number of TPA group of the porphyrin ring.

目錄
摘要…………………………………………………………………………………... I
Abstract……………………………………………………………………………….. II
目錄…………………………………………………………………………………... III
圖目錄………………………………………………………………………………... IV
表目錄………………………………………………………………………………... V
第一章 緒論……………………………………………………………………... 1
1.1. 紫質簡介……………………………………………………………... 1
1.2. 紫質取代基效應……………………………………………………... 2
1.3. 三苯胺………………………………………………………………... 10
1.4. 三苯胺取代基紫質…………………………………………………... 14
1.5. 研究目的……………………………………………………………... 19
第二章 實驗……………………………………………………………………... 21
2.1. 藥品…………………………………………………………………... 21
2.2. 儀器…………………………………………………………………... 22
2.3. 合成…………………………………………………………………... 23
2.4. 莫耳吸收係數的測定………………………………………………... 35
第三章 結果與討論……………………………………………………………... 44
3.1. UV-Vis 光譜研究……………………………………………………. 44
3.1.1. 最大吸收波長探討……………………………………………… 44
3.1.2. 半波寬探討……………………………………………………… 45
3.1.3. 吸收係數探討…………………………………………………… 49
3.2. 電化學性質研究……………………………………………………... 52
3.2.1 Porphyrin free bases 的電化學…………………………………... 52
3.2.2 Zinc porphyrins 的電化學……………………………………….. 58
3.2.3 Cobalt porphyrins的電化學……………………………………… 65
3.2.4 Cyclic Voltammograms探討……………………………………… 69
第四章 金屬紫質的電解反應…………………………………………………... 72
4.1. 金屬紫質電聚合形成雙聚合物條件及鑑定………………………... 72
4.1.1. 鋅紫質形成雙聚合物條件及鑑定……………………………… 72
4.1.2. 鈷紫質形成雙聚合物條件及鑑定……………………………… 73
4.2. 金屬紫質電聚合形成雙聚合物電化學性質……………………… 74
4.2.1. 鋅紫質電聚合形成雙聚合物電化學性質……………………… 74
4.2.2. 鈷紫質電聚合形成雙聚合物電化學性質……………………… 76
第五章 結論……………………………………………………………………... 79
未來展望……………………………………………………………………………... 80
參考文獻……………………………………………………………………………... 81

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