本論文研究分為兩部分，第一部分是SNS系列電致變色材料在電化學的應用，第二部分是含醚基架橋雙陽離子液體的物化與電化學特性探討。第一部分的研究旨在探討SNS（thiophene-pyrrole-thiophene，以下稱SNS）為主鏈架構之高分子電致變色材料。在眾多的高分子電致變色材料當中，SNS材料擁有一些重要特色，(1)氧化電位小（約 +0.7 V vs. SCE）；(2)可使用Knorr–Paal reaction為SNS材料設計官能基，用以微調其顏色；(3)可使用電化學法聚合，在ITO玻璃上有良好的附著性質。顏色大致上從黃色轉為藍色，因此是能吸收紫外光的材料，可為智慧窗增加防紫外線功能。本研究在苯環接上hexoxyl group、iso-propyl group、hexyl group、3,4-dimethyl group，以探討其性質的變化。過去沒有文獻比較SNS系列化合物在不同輔助電解質下的變色情形，然而本研究結果顯示此四個化合物分別使用TBAClO4、TBABF4這兩種輔助電解質系統製膜並進行變色實驗，發現不同輔助電解質對SNS變色材料有不同效果。第二部分是含醚基架橋雙陽離子液體的物化與電化學特性探討。離子液體是新穎的電解質，定義為在100度C下為熔融狀態的鹽類，由於其可被接受的導電度、不錯的熱穩定性、以及趨近於零的蒸氣壓，使離子液體成為一個相當受歡迎的材料，此外雙陽離子的離子液體更加提高了其熱穩定性，其結構為使用一長碳鏈連結兩個四級銨陽離子，但是相較於單陽離子，雙陽離子黏度較大、導電度較低，因此我們思考如果中間長碳鏈改為-CC-O-CC-O-CC-形式是否可以降低其黏度，從過去文獻單陽離子液體接上醚基單元皆可以降低其黏度，從實驗中得知與長碳鏈的結構比較，確實能夠大幅降低黏度。且發現此雙陽離子的雙邊不對稱的合成方法尚未被發表，也無法以過去合成不對稱的雙陽離子的方式進行合成，因此我們研究出了如何針對此結構合成不對稱雙陽離子的方法。研究中合成了五個不對稱、兩個對稱的雙陽離子離子液體進行其物理性質與電化學的探討，於303K時其中不對稱型以4-methyl-1-(2-(2-(2-(1-methyl-1H-imidazol-3-ium-3-yl)ethoxy)ethoxy)ethyl)pyridinium bis(trifluoromethylsulfonyl)amide呈現最佳的導電度。另外4-methyl-1-(2-(2-(2-(1-methyl-1H-imidazol-3-ium-3-yl)ethoxy)ethoxy)ethyl)pyridinium bis(trifluoromethylsulfonyl)amide與1-methyl-3-(2-(2-(2-(1-methylpyrrolidinium-1-yl)ethoxy)ethoxy)ethyl)-1H-imidazol-3-ium bis(trifluoromethylsulfonyl)amide呈現最低的黏度。

This study contains two major topics: one topic investigates the　electrochemical applications of 2,5-bis-(2-thienyl)-1H-pyrrole (SNS) based electrochromic materials, another topic studies the physicochemical and electrochemical properties of ether bridge based dicationic ionic liquids. The　first topic studies the electrochromism of SNS(thiophene-pyrrole-thiophene)-based conjugated polymers, the main chain of polymer backbone is SNS unit, SNS shows potential applications in electrochromism from the following reasons: (1) the oxidation potentials of the SNS-based derivatives are low (about +0.7 V vs. SCE), (2) the color of polymer films can be tuned by changing the functional group of SNS unit, (3) the SNS-based polymer film can be prepared using electropolymerization on ITO substrate, and it’s a candidate for smart window application. We propose to incorporate hexoxyl, iso-propyl group, hexyl, and 3,4-dimethyl groups in the SNS unit, and investigate the color variations of SNS-based polymer films. Few studies are reported for the electrochromism of SNS-based polymer films, so a new investigation in electrochromism could be developed in this paper. The four kinds of SNS-based polymer films are prepared using TBAClO4 and TBABF4 electrolytes, and then study the electrochromic properties, the result shows various colors with various electrolytes. The second topic illustrate the physicochemical and electrochemical characterizations of ether bridge based dicationic ionic liquids (DILs), these DILs show higher thermal stability than monocationic ILs. However, the viscosity of DILs is larger than monocationic ILs, and the conductivity of DILs is smaller than monocationic ILs. In previous studies, monocationic ILs can decrease the viscosity by introducing the ether group to the side chain of cation, in the study, ether bridge is incorporated into the dication in order to decrease the viscosity of DILs. We prepare five asymmetric DILs and investigate the physicochemicaland electrochemical properties of them, 4-methyl-1-(2-(2-(2-(1-methyl-1H-imidazol-3-ium-3-yl)ethoxy)ethoxy)ethyl)pyridinium　 bis(trifluoromethylsulfonyl)amide shows the highest conductivity at 303K. 4-methyl-1-(2-(2-(2-(1-methyl-1H-imidazol-3-ium-3-yl)ethoxy)ethoxy)ethyl)pyridinium bis(trifluoromethylsulfonyl)amide and 1-methyl-3-(2-(2-(2-(1-methylpyrrolidinium-1-yl)ethoxy)ethoxy)ethyl)-1H-imidazol-3-ium bis(trifluoromethylsulfonyl)amide the show lowest viscosity.

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