臺灣博碩士論文加值系統

本論文論及兩種帶有雙咔唑基團之單體: 2,8-di(carbazol-9-yl)dibenzothiophene (SCz)及2,8-di(carbazol-9-yl)dibenzothiophene-S,S-dioxide (SO2Cz) 的合成並利用三氯化鐵之化學氧化聚合法和電化學氧化聚合法將其聚合成螢光及電致變色的聚合物 PSCz及 PSO2Cz。我們亦合成了兩個咔唑具有第三丁基(tert-butyl)的化合物2,8-di(3,6-di-tert-butylcarbazol-9-yl)dibenzothiophene (StBCz)及2,8-di(3,6-di-tert- butylcarbazol-9-yl)dibenzothiophene-S,S-dioxide (SO2tBCz)作為性質比較之用，這四種含咔唑基的化合物的電化學和電聚合行為將加以探討，聚合物 PSCz及 PSO2Cz的光電性質如光吸收、螢光、電化學及電致變色性質等亦將在本論文中加以探討。
化學氧化聚合所製得的聚合物 PSCz及 PSO2Cz的二氯甲烷稀薄溶液顯示螢光最強的波長值在426 及524 nm 附近，而聚合物PSO2Cz 因具有分子內電荷轉移效應，所以相較於 PSCz 擁有較高的發光量子效率。這些聚合物的發光波長或顏色會受到溶劑的極性影響，在較高極性的溶劑中會有紅移的現象。
含有電解質的SCz及SO2Cz溶液經由循環伏安法在電位0.0~1.8 V之間重複掃描數圈後會在工作電極表面電聚合生成平整的高分子薄膜，然而在咔唑的活性位置上具有第三丁基的相對應化合物StBCz及SO2tBCz卻無法電聚合生成薄膜，顯示化合物SCz及SO2Cz的電聚合反應是發生在咔唑基團的3和6的位置上。電聚合生成的聚合物薄膜在電化學氧化過程中具有兩個可逆的氧化還原波峰，推測應來自於biscarbazole結構的氧化。這些聚合物薄膜也顯示了良好的電化學和電致變色穩定性，薄膜的顏色會從一種中性狀態的無色轉變為各種不同氧化態的黃色、綠色和藍色。經過多次開關切換之後，聚合物薄膜仍舊擁有良好的對比度及穿透度，顯示這些聚合物是適合用來當作電致變色元件的材料。

This thesis deals with the synthesis and characterization of two carbazole-endcapped monomers, named as 2,8-di(carbazol-9-yl)dibenzothiophene (SCz) and 2,8-di(carbazol-9-yl)dibenzothiophene S,S-dioxide (SO2Cz), and their derived polymers PSCz and PSO2Cz prepared by both chemically oxidative coupling polymerization in the presence of FeCl3 and electrochemically oxidative process. Two referenced compounds with tert-butyl blocking groups on their carbazole units, namely 2,8-di(3,6-di-tert-butylcarbazol-9-yl)dibenzothiophene (StBCz) and 2,8-di(3,6-di-tert- butylcarbazol-9-yl)dibenzothiophene-S,S-dioxide (SO2tBCz), were also synthesized for a comparative purpose. The electrochemistry and electropolymerization behaviors of these four compounds were investigated. The optoelectronic properties such as absorption, fluorescence, electrochemistry, and electrochromism of polymers PSCz and PSO2Cz were also studied in this thesis.
The dilute dichloromethane solutions of the polymers PSCz and PSO2Cz that prepared by the chemically oxidative polymerization method exhibited fluorescence maxima at around 426 and 524 nm, respectively. PSO2Cz revealed a higher fluorescence quantum yield than PSCz probably due to the intramolecular charge transfer (ICT) effect. The emission wavelength or color of the polymer solutions was dependent on the polarity of the solvent, with a red shift in the solvent of a higher polarity.
The polymeric thin films were successfully deposited onto the surface of the working electrode by repetitive cyclic voltammetry (CV) scanning of compounds SCz and SO2Cz in an electrolyte solution between 0 and 1.8 V. However, the compounds StBCz and SO2tBCz with tert-butyl blocking groups on the reactive sites of the carbazole units did not give any polymer films on the electrode upon repetitive CV scanning, indicating the electrochemical polymerization occurred through the coupling reaction between the carbazole units at the 3- or 6-position. The electrochemically generated polymer films exhibited two reversible oxidation redox couples due to successive oxidations of the biscarbazole unit. These polymer films also revealed excellent electrochemical and electrochromic stability, with coloration change from a colorless neutral state to yellow, green and blue oxidized forms. Switching ability of the polymers was evaluated by kinetic studies upon measuring the percent transmittance (%T) at their maximum contrast point, indicating that these polymers were found to be suitable materials for electrochromic devices.

CONTENTS

摘　要 i
ABSTRACT iii
ACKNOWLEDGEMENTS v
CONTENTS vi
LIST OF SCHEMES viii
LIST OF TABLES ix
LIST OF FIGURES x

CHAPTER 1 INTRODUCTION 1
CHAPTER 2 EXPERIMENTAL 4
2.1 Materials 4
2.2 Monomer Synthesis 5
2.2.1 2,8-Di(carbazol-9-yl)dibenzothiophene (SCz) 5
2.2.2 2,8-Di(carbazol-9-yl)dibenzothiophene-S,S-dioxide (SO2Cz) 6
2.2.3 2,8-Di(3,6-di-tert-butylcarbazol-9-yl)dibenzothiophene (StBCz) 7
2.2.4 2,8-Di(3,6-di-tert-butylcarbazol-9-yl)dibenzothiophene-S,S-dioxide (SO2tBCz) 8
2.3 Polymer Synthesis 9
2.3.1 Electrochemical Polymerization 9
2.3.2 Chemical Oxidative Polymerization 9
2.4 Fabrication of the Electrochromic Devices 10
2.5 Measurements 10

CHAPTER 3 RESULTS AND DISCUSSION 12
3.1 Monomer Synthesis 12
3.2 Polymer Synthesis 20
3.2.1 Electrochemical Polymerization 20
3.2.2 Chemical Oxidative Polymerization 24
3.3 Optical Properties 27
3.3.1 Absorption and Photoluminescence 27
3.3.2 Solvatochromism of Polymers 30
3.3.3 Solvatochromism of Monomers 33
3.4 Electrochemical Properties 36
3.4.1 Monomers 36
3.4.2 Electrochemically Synthesized Polymer Films 38
3.5 Spectroelectrochemical Properties 42
3.6 Electrochromic Switching and Stability 45
3.7 Electrochromic Device of PSCz 49
CHAPTER 4 CONCLUSIONS 50
REFERENCES 51

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