具不同位向對苯二胺取代基鋅紫質的合成、光譜及電化學研究

本論文主要是探討不同位向的對苯二胺(phenylenediamine, PD)單取代鋅紫質的合成、光譜與電化學性質。不同位向的對苯二胺單取代鋅紫質以循環伏安法實驗，配合滴定imidazole形成五配位的鋅紫質，觀察鋅紫質的紫質環氧化電位移動與電化學誘導氫鍵產生PD的氧化電位移動，用以比較各個氧化屬於鋅紫質或是PD；使用透光薄層電化學法(optically transparent thin-layer electrode，OTTLE)觀察鋅紫質氧化後的光譜，經由此實驗來判定紫質和PD氧化的先後順序。實驗的結果顯示，不同位向的對苯二胺單取代鋅紫質會因PD的位向不同，產生紫質和PD氧化順序的差異。PD取代基造成間位和對位的鋅紫質，第一個氧化為PD的氧化，第二個氧化為紫質環的氧化，而PD取代基造成鄰位的鋅紫質，則是紫質環的氧化會先於PD分子的氧化。

關鍵字

對苯二胺；鋅紫質；電化學；光譜電化學；氫鍵

並列摘要

Variously orientated phenylenediamine (PD) mono-substituted zinc porphyrins were synthesized. The electrochemical and spectral properties of these zinc porphyrins were studied. In the presence of imidazole, five coordinated zinc porphyrins could be formed; meanwhile, it could cause the shift of oxidation potential of zinc porphyrin. When the PD moiety was oxidized, imidazole could rapidly form hydrogen bonding with oxidized PD, and could cause potential inversion. Spectroelectrochemical method, optically transparent thin-layer electrode (OTTLE), was used to monitor the changes of absorption spectra of the zinc porphyrins when potentials were applied. Cyclic voltammetry and OTTLE can be estimated for the priority of oxidation potentials between the porphyrin ring and the PD substitutent. The first oxidation of the meta- and para-substituted zinc porphyrins is at PD moiety, and the second of which is at the porphyrin ring. But the situation of ortho-substituted zinc porphyrins is quite different.