以azine為架橋基的雙二茂鐵分子衍生物的合成與離子辨識行為探討

Synthesis and Recognition Behavior of Bisferrocene Derivatives Comprising Azine Moiety

張佩雯(Pei-Wen Chang)

指導教授 ： 林美靜

朝陽科技大學/理工學院/應用化學系/碩士(2012年)

摘要

本研究主要是利用azine基團與二茂鐵分子，合成單核分子與雙核分子二茂鐵衍生物，並藉由增長分子鏈段觀察兩端二茂鐵電活性中心的電子溝通情形，同時，將化合物28、31、38進行光化學現象探討與金屬離子辨識實驗。
在循環伏安法之電化學研究中，化合物28、31、38的二茂鐵基團的半波電位都出現在0.67 V，微分脈衝伏安法 (differential pulse voltammetry)顯示化合物31中兩端的二茂鐵分子在同一個電位進行氧化，含炔基的化合物38則呈現兩個氧化峰，代表炔基的鍵結可增加分子鏈段的共軛性，有助於兩端二茂鐵分子的電子溝通。
在UV-vis吸收光譜圖中，化合物28、38、31主要吸收峰有兩個，350 nm 與500 nm附近，分別是來自於架橋基的π-π* 、二茂鐵分子中鐵原子對配位基價電荷的轉移。由光譜圖觀察到π共軛系統增加，會造成架橋基中π-π* 的吸收產生紅位移、強度上升的現象。
三個化合物都對汞 (II) 離子有明顯的辨識行為。在UV-vis光譜圖中，Hg (II) 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 Hg (II) 離子配位所造成的結果。化合物38與汞 (II) 離子進行Job’s plot實驗，顯示化合物38與汞 (II) 離子以1：1比例進行錯合，錯合常數約4.69 × 103 M-1.

關鍵字

離子辨識 ； azine架橋基 ； 雙二茂鐵 ； 電化學

並列摘要

This research connecting the ferrocene molecules through azine group and phenyl group, ethynyl moiety to afford a mononuclear and binuclear compounds 28, 31, 38. We study the relationship of electronic communication with the elongation of the molecular chain. Also, the photochemical behavior and the recognition of metal ions were presented.

The cyclic voltammogram of 28、31、38 shows that all the ferrocene moieties exhibit the E1/2 at 0.67 V. The differential pulse voltammetry presents that both the ferrocene moiety in the compound 31 oxidized at the same potential. However, when incorporate the ethynyl into the main china of the molecular, compound 38 exhibit two oxidation waves, which means that insertion of ethynyl will perturb the electronic properties of the molecule.

Compound 28, 31, 38 showed two main absorption peaks at 350 nm and 500 nm in the UV-vis absorption spectra, which are ascribable to the azine-bridge and the metal-to ligand charge transfer from ferrocene. We also observed that the enhanced of the π conjugation system, it will cause a red shift of the absorption peak of π-π *transition.

In the recognition behavior, when Hg2+ is added to 28, 31, 38, all the absorption peak produce an obvious red shift, which may be the result of the coordination of azine group with the metal. By the titration experiment of compound 38 and Hg (II), the data indicated a 1 : 1 binding model and an association constant of 4.69 × 103 M-1in solution.

並列關鍵字

Bisferrocene ； azine moiety ； Recognition ； electrochemical

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