新型特羅格鹼三芳香胺材料之合成及其電致變色性質探討

Abstract

本論文分為四個章節，第一章為總體緒論，介紹功能性高分子、電致變色之發展與改良，以及Tröger's base的結構與化學特性。接著在第二章的研究中，成功合成並鑑定出了一個新型的含TB單元的三苯胺二胺單體TBTPA-NH2，並利用其醯胺衍生物TBTPA-M作為模型分子，透過循環伏安法(CV)、微分脈衝伏安法(DPV)及能斯特分析以研究此新型電活性分子之電致變色行為表現。此外，我們利用此新型單體製備成自具微孔的聚醯胺高分子PTBTPA，透過量測密度與電化學阻抗圖譜證明其微孔性，並以此研究自具微孔性質對於反應時間與電致變色表現之影響。而在第三章的研究當中，一系列對位胺基取代之三苯胺衍生物展現出低氧化電位與多段變色之特性，透過循環伏安法(CV)與光譜電化學量測，其電化學性質與氧化機制被完整闡述。此外，此一系列分子展現出高度電化學穩定性，所製備之電致變色元件性質已透過多種電化學量測方式記錄，展現出具有高對比度與長時間穩定之成效。最後，第四章總結了實驗結果，我們發現TB單元可形成自具微孔結構，增加了高分子的自由體積，此特性既提高了響應速度也降低了驅動電壓。此外，對位胺基取代的TPA分子在電致變色元件中表現出優異的穩定性與著色效率，提供了一種方式以製造多段變色、高效之電致變色元件。

This study has been divided into four chapters. Firstly, a general introduction was provided in chapter 1, introducing high-performance polymers, the development and enhancement of electrochromism (EC), and Tröger's base (TB) chemistry. Secondly, in chapter 2, a novel electroactive diamine monomer, TBTPA-NH2, was synthesized and characterized. To investigate the electrochemical properties of this molecule, an amide-type model compound, TBTPA-M, was synthesized for the experiments. With cyclic voltammetry (CV), differential pulse voltammetry, and Nernstian analysis, the EC properties of this monomer with TB moiety were recorded. Furthermore, an intrinsic microporous polyamide, PTBTPA, was prepared from this monomer. The porosity was confirmed by film density and electrochemical impedance spectroscopy (EIS). Measurements such as cyclic voltammetry, spectroelectrochemistry, and switching response were taken to evaluate the benefits of intrinsic microporous moieties. The electrochemical parameters of PTBTPA were recorded, showing better results. Then, in chapter 3, the electrochemical properties of a series of para-amino substituted TPA derivatives were investigated. The multi-electrochromic and low-driving-voltage attributes became the advantages for electrochromic applications. Moreover, these amino substituted TPA revealed unexpectedly high stability in long-term measurement. The electroactive TPA chromophores were further fabricated as electrochromic devices (ECDs). The oxidation mechanism and EC properties were clarified by the measurements including cyclic voltammetry, spectroelectrochemistry, and switching response Finally, the experiment results were summarized in chapter 4. We found out that the introduction of TB moiety created micropores which increased the free volume of polymers, enhancing the response speed and reducing the driving voltage. Additionally, the electrochemical properties of para-amino substituted TPA derivatives were thoroughly studied. The ECDs revealed superior stability and coloration efficiency, providing a facile method of fabricating multi-electrochromic, energy-efficient devices.