合成含香豆素的二茂鐵衍生物與金屬辨識研究

Synthesis and Metal Recognition Behavior Studies of Coumarin Substituted Ferrocene Derivatives

黎祐誠(You-chang Li)

指導教授 ： 林美靜

朝陽科技大學/理工學院/應用化學系/碩士(2014年)

摘要

本研究主要是利用azine 基團將香豆素發光團與二茂鐵單元進行連結，同時我們也在二茂鐵單元上進行不同取代基的修飾，經由NMR、IR及質譜圖證明，成功合成出新的化合物S與S1。化合物S對汞離子有明顯的辨識行為。在UV-vis 光譜圖中，汞離子的加入，會導致吸收峰產生紅位移，推測是化合物中的azine基團與香豆素對汞離子配位所造成的結果。化合物S與汞離子進行Job’s plot 實驗，顯示化合物S與汞離子以1：1 比例進行錯合，結合常數KS為5.51×104 M-1。在電化學的研究上，化合物S、S1都呈現一個可逆的氧化還原波，且隨著二茂鐵單元上的取代基不同而改變鐵原子的半波電位(化合物S，E1/2 = 0.6445 V；化合物S1，E1/2 = 0.9060 V)，由此現象我們認為香豆素發光團與二茂鐵單元之間有電子溝通的情形。化合物S在室溫下呈現微弱的放光行為(λex= 320 nm，λem= 390 nm)，當加入Cu2+後，螢光強度有明顯上升的趨勢，我們推測在化合物S中，二茂鐵分子提供軌域進行消光；而Cu2+為氧化劑，使二茂鐵單元中的Fe2+ 氧化成Fe3+，導致二茂鐵基團的消光機制被抑制，因此可以觀察到香豆素典型的螢光現象。

關鍵字

化學感測器 ； 二茂鐵 ； 香豆素

並列摘要

This study use azine group to linked coumarin group and ferrocene unit, and we are also makes different modified on the ferrocene unit. Both compound S and S1were characterized by NMR, IR and Mass spectra to confirm the structure. Compound S shows obviously recognize behavior with mercury ions. In the UV-vis spectra, when Hg ions added in the solution of S, the absorption band will lead to a red shift, which is speculated the result of coordination of Hg ion with azine group and coumarin unit. In Job''s plot experiments, the binding mode of compound S and mercury ions is 1: 1, and the binding constant is 5.51 × 104 M -1. In the study of electrochemical analysis, both compound S and S1 presented a reversible redox waves, and the half-wave potential of Fe atoms varied with the different substitution on the ferrocene unit (compound S, E1/2 = 0.6445 V; compound S1, E1/2 = 0.9060 V), which mean that there are electronic communication between the coumarin chromophore with ferrocene unit. Compound S shows weak emission at room temperature (λex = 320 nm, λem = 390 nm), however, when we added Cu2+ to the solution of S, the fluorescence intensity significantly increasing. We hypothesized that in compound S, the ferrocene subunit provide an orbital to quench the fluorescence of the chromophore, after the addition of Cu2+, which acts as the oxidant, make Fe2+ oxidized to Fe3+, and suppressed the quench path of ferrocene groups, and we can observe the typical fluorescence of coumarin group.

並列關鍵字

Chemosensor ； Ferrocene ； Coumarin

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