釕胺基菲羅啉衍生物之製備和應用

Abstract

有鑒於含釕配位化合物，如Ru(bpy)32+，具有光電化學的應用潛力，本論文合成5-胺基菲羅啉（5-aminophenanthroline，簡稱NH2-phen）含釕化合物，Ru(bpy)2(phen-NH2)2+和Ru(phen-NH2)32+，並藉由電化學修飾法將之修飾於電極表面，以觀察其電化學發光行為(Electrochemiluminescence，簡稱ECL)。實驗結果顯示：在液相中，[Ru(bpy)2(NH2-phen)]2+可產生ECL，但比Ru(bpy)32+弱，而[Ru(NH2-phen)3]2+則不會產生ECL。若將[Ru(bpy)2(NH2-phen)]2+和[Ru(NH2-phen)3]2+固定於電極上，則二者都難產生ECL。我們也嘗試將其固定於奈米碳管上，然而其ECL也不甚明顯。雖然如此，我們嘗試利用[Ru(bpy)2(NH2-phen)]2+作為敏光劑，以催化Phenothiazine進行氧化聚合反應。實驗結果顯示[Ru(bpy)2(NH2-phen)]2+可有效氧化Thionine，使之成為聚合物。

Ruthenium trisbipyridine (Ru(bpy)32+) is an effective light-emitting reagent, emitting red light under photochemical and electrochemical excitations. In the light of this, we synthesized ruthenium trisbidentates, [Ru(bpy)2(NH2-phen)]2+ and[Ru(NH2-phen)3]2+, for ECL investigation. Experimental results showed that in CH3CN, [Ru(bpy)2(NH2-phen)]2+ could emit light during anodic oxidation if tripropylamine was in the presence. In contrast, [Ru(NH2-phen)3]2+ did not produce similar result in this respect. [Ru(bpy)2(NH2-phen)]2+ and [Ru(NH2-phen)3]2+ were also immobilized on electrodes for ECL analysis via anodic polymerization and diazotization-reduction processes. Unfortunately, both failed to produce ECL. Despite this, [Ru(bpy)2(NH2-phen)]2+ showed potential in photo-induced oxidative polymerization for phenothiazines. In aerated solutions, thionine chloride formed polymer under the photosensitization of [Ru(bpy)2(NH2-phen)]2+, which might be useful for photolithographic applications.