臺灣博碩士論文加值系統

兩種以三苯基胺或N-苯基咔唑作為核心結構並含兩個咔唑封端的單體 4,4’-Di(carbazol-9-yl)-4”-methoxytriphenylamine (TPA-2Cz) 及 3,6-Di(carbazol-9- yl)-N-(4-methoxyphenyl)carbazole (PhCz-2Cz) 係經由一個眾所皆知的化學從容易取得的試劑製備而成。我們探討這兩個單體衍生物的電化學和電聚合反應，並與咔唑基的活性位置具有tert-butyl取代基的類似單體進行了比較。將單體溶在具有電解質的溶液中，經過循環伏安（CV）重複的掃描數圈後，高分子薄膜會在ITO/玻璃表面逐漸生成。這些塗佈在ITO/玻璃表面的高分子薄膜表現出可逆的電化學氧化還原過程且伴隨著明顯的顏色變化。這些薄膜的電致變色行為可藉由光譜電化學清楚地解釋，多次開關測試研究則用來評估電聚合薄膜的電致變色穩定性。此外，我們也使用氯化鐵作為氧化劑的化學氧化聚合法將這兩種單體聚合成高分子，這些高分子的溶液和固態薄膜在受紫外光激發時會發射藍色螢光。

Two carbazole end-capped monomers containing triphenylamine or N-phenylcarbazole as an interior core, namely 4,4’-di(carbazol-9-yl)- 4”-methoxytriphenylamine (TPA-2Cz) and 3,6-di(carbazol-9-yl)-N-(4-methoxy- phenyl)carbazole (PhCz-2Cz), were prepared by a well-known chemistry from readily available reagents. The electrochemistry and electropolymerization of these two monomers were investigated and compared with those of structurally similar analogues with tert-butyl groups attaching on the active sites of the end-capped carbazole units. The polymeric films were built onto ITO/glass surface by repetitive cyclic voltammetry (CV) scanning of the monomer solutions containing an electrolyte. The electropolymerized films exhibited reversible electrochemical oxidation processes and strong color changes upon electro-oxidation, which can be switched by potential modulation. The remarkable electrochromic behavior of the film was clearly interpreted on the basis of spectroelectrochemical studies, and the electrochromic stability was evaluated by the electrochromic switching studies. In addition, the polymers of TPA-2Cz and PhCz-2Cz were also prepared by oxidative coupling polymerization using FeCl3 as an oxidant. Their solutions and solid films emitted blue fluorescence upon exposure to UV light.

CONTENTS
摘 要 i
ABSTRACT ii
ACKNOWLEDGEMENTS iv
CONTENTS v
LIST OF SCHEMES vii
LIST OF TABLES viii
LIST OF FIGURES ix


CHAPTER 1 INTRODUCTION 1
CHAPTER 2 EXPERIMENTAL 3
2.1 Materials and Instrumentation 3
2.1.1 Materials 3
2.1.2 Instrumentation 4
2.2 Monomer Synthesis 5
2.2.1 3,6-Di(carbazol-9-yl)-N-(4-methoxyphenyl)carbazole (3) 5
2.2.2 4,4’-Di(carbazol-9-yl)-4’’-methoxytriphenylamine (3’) 6
2.2.3 3,6-Di(3,6-di-tert-butylcarbazol-9-yl)-N-(4-methoxyphenyl)carbazole (4) 7
2.2.4 4,4’-Di(3,6-di-tert-butylcarbazol-9-yl)-4’’-methoxytriphenylamine (4’)... 8
2.3 Polymer Synthesis 9
2.3.1 Electrochemical Polymerization 9
2.3.2 Chemical Polymerization 9
CHAPTER 3 RESULTS AND DISCUSSION 10
3.1 Monomer Synthesis 10
3.2 Polymer Synthesis 18
3.2.1 Electrochemical Polymerization 18
3.2.2 Chemical Polymerization 19
3.3 Optical Properties 21
3.3.1 Monomers 21
3.3.2 Polymer 22
3.4 Electrochemical Properties 24
3.4.1 Monomers 24
3.4.2 Electrochemically Synthesized Polymer Films 24
3.5 Spectroelectrochemical and Electrochromic Properties 30
CHAPTER 4 CONCLUSIONS 36
REFERENCES 37

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