具硝基苯取代基紫質的合成與電化學性質研究

Synthesis and Electrochemical Studies of Porphyrins Substituted with Nitrobenzenes

林毅青(Yi-Ching Lin)

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(2008年)

摘要

本論文主要是探討具對稱與不對稱meso-硝基苯取代基紫質的合成與電化學性質。將具對稱與不對稱的meso-硝基苯取代基紫質加入鋅離子成為鋅紫質，並分別合成硝基位於ortho, meta和para三種不同位置的同分異構物，使用循環伏安法觀察此類化合物的氧化和還原電位的改變，藉以推論硝基在苯環的位置不同時對紫質環的影響。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。
另外以滴定1,3-二苯基脲(1,3-diphenyl urea)的方式，使1,3-二苯基脲與硝基形成hydrogen-bond，會導致硝基的還原電位改變，藉以釐清此類紫質在還原部份複雜的電化學現象。另外再以透光薄層電化學法(optically transparent thin-layer electrode, OTTLE)觀察紫質經過還原後的光譜確定還原位置。期望判斷各個還原各為紫質環或是硝基所屬。

關鍵字

紫質 ； 鋅紫質 ； 循環伏安法 ； 透光薄層電化學法 ； 1,3-二苯基脲

並列摘要

We have synthesized symmetric and asymmetric free base porphyrins and their zinc complexes containing nitrophenyl and tolyl substituents. Electron-withdrawing substituents on the phenyl rings exert different electronic effects on the porphyrin core, depending on the ortho, para and meta positions. Cyclic voltammetry and spectroelectrochemistry was used to monitor the difference of redox potential and absorption spectra of those compounds.
In addition, the cyclic voltammograms porphyrin and nitrophenyl group were overlapped in the reductive, therefore the electrochemical behaviors become complex. In order to resolve these overlapped problem, so we use titration method in cyclic voltammetry. 1,3-diphenylurea can form hydrogen bonding with nitrophenyl group and form anodic shift of the reductive potential. We hope this method can distinguish those potential be caused of someone.

並列關鍵字

porphyrins ； Zinc porphyrins ； Cyclic voltammetry ； optically transparent thin-layer electrode(OTTLE) ； 1.3-diphenyl urea

參考文獻

參考文獻

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