取代基效應影響對苯二胺鋅紫質與咪唑作用之電化學研究

Electrochemical Studies of the Substituent Effects on the Interactions between Phenylenediamine Substituted Zinc Porphyrins and Imidazole

陳冠伶(Guan-Ling Chen)

指導教授 ： 蘇玉龍

國立暨南國際大學/科技學院/應用化學系/碩士(2015年)

https://doi.org/10.6837/NCNU.2015.00200

摘要

本論文研究不同推、拉性質的取代基對於對苯二胺鋅紫質與咪唑作用影響之電化學，利用光譜、循環伏安法及光譜電化學法觀察咪唑與對苯二胺鋅紫質的作用。
光譜滴定實驗中，隨著咪唑配位基濃度的增加，使對苯二胺鋅紫質由四配位形成五配位的形式，造成吸收光譜的改變。循環伏安圖中，對苯二胺鋅紫質均可進行四個電子可逆的氧化，而取代基的性質會影響其氧化還原電位。含有咪唑的對苯二胺鋅紫質溶液中，取代基對苯二胺氧化後，咪唑會從鋅紫質中心金屬轉移至取代基，與取代基形成氫鍵。使用光譜電化學法觀察光譜的變化，判定紫質與取代基氧化的先後順序。本研究中最特別的為ZnTDCPP-PD，從循環伏安法的實驗結果，推測咪唑分子可穿梭於鋅紫質與其對苯二胺取代基之間。

關鍵字

鋅紫質 ； 對苯二胺 ； 循環伏安法 ； 氫鍵 ； 電化學誘導氫鍵 ； 光譜電化學

並列摘要

A serious of phenylenediamine(PD)-substituted zinc porphyrins with different electron-withdrawing and electron-donating groups have reported in this work. Their electrochemical properties were investigated by UV-Vis spectra, cyclic voltammetry (CV), and optically transparent thin-layer electrode (OTTLE).
Imidazole is an common axial ligand of metalloporphyrin. In the UV-Vis spectrum, the spectral change between four and five coordinated zinc porphyrins were monitored while imidazole added. CVs showed that all those zinc porphyrins have four redox couples in the oxidative aspect. Controlling the oxidative potential would dominate the move of imidazole. Because the affinity of oxidized species is larger than the neutral ones. By using CV and OTTLE, we verified that imidazole has a shuttling behavior between central metal and oxidized PD moiety.

並列關鍵字

zinc porphyrin ； p-phenylenediamines ； cyclic voltammetry ； hydrogen bonding ； electrochemically induced hydrogen bonding ； spectroelectrochemistry

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