臺灣博碩士論文加值系統

本論文首先合成代碼分別為T-3(NHCO-TPA)、T-3(NHCO-NPC)、T-3(CONH-TPA)及 T-3(CONH-NPC)四種以三苯胺為核心經由醯胺基 (−NHCO− 或 −CONH−) 連接三苯胺 (triphenylamine; TPA) 或N-苯基咔唑(N-phenylcarbazole; NPC) 末端基的星狀分子，並探討它們的電化學和電聚合性質。這些星狀分子的氧化電位與氧化態結構的穩定性受到醯胺鍵方向及末端三芳香胺結構的影響。藉由反覆數次的循環伏安掃描探討這些星狀化合物的電化學及電聚合性質，其中T-3(NHCO-TPA) 及T-3(CONH-NPC)在溶有四丁基銨次氯酸鹽(tetrabutylammonium perchlorate)的二氯甲烷的溶液中經由反覆數次的循環伏安掃描可在ITO電極表面電聚合生成電活性的高分子薄膜。這些電聚合薄膜具有可逆的電化學氧化還原反應並且伴隨著顯著的顏色變化。這些高分子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。
在論文的第二部分，我們利用4-胺基三苯胺(4-aminotriphenylamine; TPA-NH2)分別與芳香族二酸酐pyromellitic dianhydride (PMDA)、 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) 及 3,4,9,10-perylenetetracarboxylic dianhydride (PTDA)縮合反應備製三個雙三苯胺二醯亞胺化合物[bis(triphenylamine)-diimide] TPA-PMDI、TPA-NTDI及TPA-PTDI。這些末端含三苯胺的二醯亞胺單體可在電解液中透過三苯胺基團的電氧化偶合反應於電極表面上生成聚(芳香胺-醯亞胺)薄膜TPA-PMPI、 TPA-NTPI及 TPA-PTPI。這些電沉積的高分子薄膜的循環伏安圖顯示它們具有兩性的氧化還原行為，在陽極掃描時出現一對可逆的氧化還原峰，半波電位(E1/2)約在0.99−1.02 V之間；在陰極掃描時則出現兩對氧化還原峰。這些電聚合薄膜具有多顏色的陰極與陽極變色行為。我們亦以這些電聚合薄膜作為電活性層製作成電致變色元件，評估它們在電致變色元件應用的可能性。

In the first part of this thesis, four star-shaped molecules with triphenylamine (TPA) core through the amide group (−NHCO− or −CONH−) linked to the terminal triphenylamine or N-phenylcarbazole (NPC) unit, coded as T-3(NHCO-TPA), T-3(NHCO-NPC), T-3(CONH-TPA), and T-3(CONH-NPC), were synthesized and their electrochemistry and electropolymerization behaviors were investigated. The oxidation potential and the stability of the oxidized forms of the starbursts are affected by the orientation of amide linkage and the structure of terminal triarylamino group. Robust polymeric films could be built onto ITO/glass surface by repetitive cyclic voltammetry of the monomer solutions of T-3(NHCO-TPA) and T-3(CONH-NPC) in dichloromethane containing tetrabutylammonium perchlorate as supporting electrolyte. The electrodeposited films exhibited reversible electrochemical 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 the second part of this thesis, three bis(triphenylamine)-diimide compounds, TPA-PMDI, TPA-NTDI and TPA-PTDI, were synthesized from condensation of 4-aminotriphenylamine with pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) and 3,4,9,10-perylenetetracarboxylic dianhydride (PTDA), respectively. Redox-active poly(arylamine-imide) films coded as TPA-PMPI, TPA-NTPI, and TPA-PTPI could be electrodeposited robustly on the electrode surface from the bis(triphenylamine)-diimides in an electrolyte solution via the oxidative coupling reactions between TPA terminal groups. The cyclic voltammograms of these electrodeposited films showed an ambipolar redox behavior, with a reversible redox couple at half wave potential (E1/2) of 0.99−1.02 V during the anodic scanning and two pairs of redox waves during cathodic scanning. The polymer films exhibited multicolored anodic and cathodic coloring. Electrochromic devices using the electropolymerized films as active layers were also fabricated as preliminary investigations for electrochromic applications.

CONTENT
摘要 i
ACKNOWLEDGEMENTS iii
ABSTRACT iv
CONTENT vi
LIST OF SCHEMES viii
LIST OF TABLES ix
LIST OF FIGURES x

Part I　
ABSTRACT 2
CHAPTER 1 INTRODUTION 3
CHAPTER 2 EXPERIMENTAL 6
2.1 Materials and Instrumentation 6
2.1.1 Materials 6
2.1.2 Instrumentation 6
2.2 Monomer Synthesis 7
2.2.1 T-3(NHCO-TPA) 7
2.2.2 T-3(NHCO-NPC) 8
2.2.3 T-3(CONH-TPA) 9
2.2.4 T-3(CONH-NPC) 10
2.3 Synthesis of Model Compounds 10
2.3.1 T-3(NHCO-Ph) 10
2.3.2 T-3(CONH-Ph) ………. 11
2.4 Electrochemical Polymerization 12
2.5 Fabrication of Electrochromic Devices 12
CHAPTER 3 RESULTS AND DISCUSSION 14
3.1 Monomer Synthesis 14
3.2 Electrochemical Activity and Polymerization of Monomers 27
3.3 Optical Properties 36
3.4 Redox Response of the Polymer Films 38
3.5 Electro-optical Properties of Polymers 43
3.6 Electrochromic Switching 46
3.7 Electrochromic Device 51
CHAPTER 4 CONCLUSIONS 53
REFERENCES 54
Part II
ABSTRACT 62
CHAPTER 1 INTRODUCTION 63
CHAPTER 2 EXPERIMENTAL 66
2.1 Materials and Instrumentation 66
2.1.1 Materials 66
2.1.2 Instrumentation 67
2.2 Monomer Synthesis 68
2.2.1 N,N’-Bis(4-diphenylaminophenyl)pyromellitimide (TPA-PMDI) 68
2.2.2 N,N’-Bis(4-diphenylaminophenyl)naphthalene-1,4,5,8-dicarboximide (TPA-NTDI) 68
2.2.3 N,N’-Bis(4-diphenylaminophenyl)perylene-3,4,9,10-dicarboximide (TPA-PTDI) 69
2.3 Synthesis of Model Compounds 69
2.3.1 N-(4-diphenylaminophenyl)phthalimide (M1) 70
2.3.2 N-(4-diphenylaminophenyl)-1,8-naphthalimide (M2) 70
2.4 Electrochemical Polymerization 71
2.5 Fabrication of Electrochromic Devices 71
CHAPTER 3　RESULTS AND DISCUSSION 73
3.1 Monomer Synthesis 73
3.2 Electrochemical Activity of Monomers 83
3.3 Optical Properties 88
3.4 Redox Response of Polymers 90
3.5 Spectroelectrochemical Properties 96
3.6 Electrochromic Switching 102
3.7 Electrochromic Devices 108
CHAPTER 4 CONCLUCSIONS 110
REFERENCES 111

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