臺灣博碩士論文加值系統

本論文在探討利用電化學聚合法合成含10,11-二氫化-5H-二苯[b,f]氮呯(10,11-dihydro-5H-dibenz[b,f]azepine)結構的聚(芳香胺-醯亞胺)與聚(芳香胺-醯胺)及其電化學及電致變色特性。
在論文的第一部分，首先將含二苯氮呯結構的一胺5-(4-aminophenyl)-10,11-dihydro-5H-dibenz[b,f]azepine與pyromellitic dianhydride (PMDA)、naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTDA)和perylene-3,4,9,10-tetracarboxylic dianhydride (PTDA)縮合成三種電活性的二醯亞胺單體，N,N’-bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]pyromellitimide (AZTPA-PMDI)、N,N’-bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]naphthalene-1,4,5,8-tetracarboxylic diimide (AZTPA-NTDI)和N,N’-bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]perylene-3,4,9,10-tetracarboxylic diimide (AZTPA-PTDI)。將這些二醯亞胺單體溶於Bu4NClO4/CH2Cl2中進行循環伏安掃描可直接在ITO電極表面生成聚(芳香胺-醯亞胺)薄膜 AZTPA-PMPI、AZTPA-NTPI及AZTPA-PTPI。這三種聚合物薄膜皆具有兩性的電化學氧化還原行為與多種顏色變化，在陽極掃描時出現一對可逆的氧化還原峰，在陰極掃描時則出現兩對氧化還原峰。藉由開關測試了解薄膜的電致變色穩定性。我們也以這些電聚合薄膜為電活性材料製成簡易的電致變色元件，評估其在電致變色領域應用的可能性。
在論文的第二部分，一種新型含二苯氮呯及三苯胺結構的二胺化合物4,4’-diamino-4”-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine (AZTPA-2NH2)是由5-(4-aminophenyl)-10,11-dihydro-5H-dibenz[b,f]azepine與p-fluoronitrobenzene的縮合及二硝基中間產物的還原製得。AZTPA-2NH2 分別與4-羧基三苯胺(4-carboxytriphenylamine) 和N-(4-羧苯基)咔唑 [N-(4-carboxyphenyl)carbazole]進行縮合反應製得兩種具有二苯氮呯-三苯胺核心結構及兩個三苯胺(triphenylamine; TPA)或N-苯基咔唑(N-phenylcarbazole; NPC)末端基的電活性單體AZTPA-(TPA)2及AZTPA-(NPC)2。 將這兩個單體溶於0.1 M Bu4NClO4/CH2Cl2的電解液中，於0.0到1.5 V間進行循環伏安掃描，末端的TPA或NPC基團會產生電化學偶聯反應直接在ITO玻璃電極的表面上沉積電活性聚合物薄膜。這兩種電化學生成的聚合物薄膜都顯示出可逆的氧化還原過程及明顯的顏色變化，可以從無色的中性態轉變成黃綠色或藍色的氧化態。這兩種電致變色薄膜具備良好的電致變色穩定性及著色效率。我們以電聚合薄膜作為活性層製作電致變色元件，評估它們在研究電致變色的應用潛力。

This thesis deals with the electrochemical synthesis and electrochemical and spectroelectrochemical characterization of poly(arylamine-imide)s and poly(arylamine-amide)s containing the 10,11-dihydro-5H-dibenz[b,f]azepine unit.
In the first part of this thesis, three electroactive diimide monomers N,N’-bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]pyromellitimide (AZTPA-PMDI), N,N’-bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]naphthalene-1,4,5,8-tetracarboxylic diimide (AZTPA-NTDI), and N,N’-bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]perylene-3,4,9,10-tetracarboxylic diimide (AZTPA-PTDI) were synthesized from condensation of 5-(4-aminophenyl)-10,11-dihydro-5H-dibenz[b,f]azepine with pyromellitic dianhydride (PMDA), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTDA), and perylene-3,4,9,10-tetracarboxylic dianhydride (PTDA), respectively. Poly(arylamine-imide) films coded as AZTPA-PMPI, AZTPA-NTPI, and AZTPA-PTPI could be electrodeposited on the ITO-glass surface by repetitive cyclic voltammetry (CV) scanning of the diimide solutions in an electrolyte solution of Bu4NClO4/CH2Cl2. The CV diagrams of the electrodeposited films showed an ambipolar redox behavior, with a reversible redox couple during the anodic scanning and two pairs of irreversible redox waves during cathodic scanning. The polymer films displayed multicolored anodic and cathodic coloring. Simple electrochromic devices using the electropolymerized films as electroactive layers were also fabricated as preliminary investigations for electrochromic applications.
In the second part of the paper, a new aromatic diamine, namely 4,4’-diamino-4”-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine (AZTPA-2NH2), was successfully synthesized from the fluoro-displacemment of p-fluoronitrobenzene with 5-(4-aminophenyl)-10,11-dihydro-5H-dibenz[b,f]azepine, followed by Pd/C-catalyzed hydrazine reduction of the dinitro intermediate. Two electroactive monomers AZTPA-(TPA)2 and AZTPA-(NPC)2 with (10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine core linked via amide group to two triphenylamine (TPA) or N-phenylcarbazole (NPC) terminal units were prepared by the condensation reaction of AZTPA-2NH2 with 4-carboxytriphenylamine and N-(4-carboxyphenyl)carbazole, respectively. These two monomers were dissolved in 0.1 M Bu4NClO4/CH2Cl2 and subjected to repetitive CV scanning between 0 and 1.5 V. Electroactive polymer films could be electrodeposited on the electrode surface via the oxidative coupling reactions between TPA or NPC radical cations. Both electro-generated polymer films exhibit reversible redox processes, displaying strong color changes from a colorless neutral state to yellow-green or blue oxidation state. The polymer films display good electrochromic stability and high color efficiency. Electrochromic devices using the electrodeposited films as active layers were also fabricated and tested for electrochromic applications.

摘要 i
ABSTRACT iii
ACKNOWLEDGEMENTS vi
CONTENTS vii
LIST OF SCHEMES x
LIST OF TABLES xi
LIST OF FIGURES xii
CHAPTER 1 1
INTRODUCTION 1
CHAPTER 2 12
2.1 Materials and Instrumentation 12
2.1.1 Materials 12
2.1.2 Instrumentation 13
2.2 Monomer Synthesis of Chapter 3 14
2.2.1 5-(4-Nitrophenyl)-10,11-dihydro-5H-dibenz[b,f]azepine (AZTPA-NO2) 14
2.2.2 5-(4-Aminophenyl)-10,11-dihydro-5H-dibenz[b,f]azepine (AZTPA -NH2) 15
2.2.3 N,N’-Bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]pyromellitimide (AZTPA-PMDI) 16
2.2.4 N,N’-Bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]naphthalene-1,4,5,8-tetracarboxylic diimide (AZTPA-NTDI) 16
2.2.5 N,N’-Bis[4-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)phenyl]perylene-3,4,9,10-tetracarboxylic diimide (AZTPA-PTDI) 17
2.3 Monomer Synthesis of Chapter 4 18
2.3.1 4,4’-Dinitro-4”-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine (AZTPA-2NO2) 18
2.3.2 4,4’-Diamino-4”-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine (AZTPA-2NH2) 18
2.3.3 4,4’-Bis(4-diphenylaminobenzamido)-4”-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine (AZTPA-(TPA)2) 19
2.3.4 4,4’-Bis[4-(carbazol-9-yl)benzamido]-4”-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine (AZTPA-(NPC)2) 20
2.3.5 4,4’-Dibenzamido-4”-(10,11-dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine (AZTPA-(Ph)2) 21
2.3.6 N,N-Bis(4-aminophenyl)-N’,N’-diphenyl-1,4-phenylenediamine (TPPDA-2NH2) 22
2.3.7 N,N-Bis[4-(4-diphenylaminobenzamido)phenyl]-N’,N’-diphenyl-1,4-phenylenediamine (TPPDA-(TPA)2) 22
2.3.8 N,N-Bis{4-[(carbazol-9-yl)benzamido]phenyl}-N’,N’-diphenyl-1,4-phenylenediamine (TPPDA-(NPC)2) 23
2.3.9 N,N-Bis(4-benzamidophenyl)-N’,N’-diphenyl-1,4-phenylenediamine (TPPDA-(Ph)2) 24
2.3.10 Triphenylamine (TPA) 24
2.5 Electrochemical Polymerization 25
2.6 Fabrication of Electrochromic Devices 25
CHAPTER 3 27
Electrosynthesis of Electrochromic Polymer Films from Arylene Diimides of 5-(4-Aminophenyl)-10,11-dihydro-5H-dibenz[b,f]azepine 27
3.1 Monomers synthesis 27
3.2 Electrochemical Activity of Monomers 38
3.3 Optical Properties 46
3.4 Electrochemical Properties of the Polymer Films 48
3.5 Spectroelectrochemistry of the Polymers 56
3.6 Electrochromic Switching 66
3.7 Electrochromic Devices 71
CHAPTER 4 74
Electrosynthesis of Electrochromic Properties of Poly(amide-triarylamine)s Containing 10,11-Dihydro-5H-dibenz[b,f]azepin-5-yl)triphenylamine Units 74
4.1 Monomer Synthesis 74
4.2 Electrochemical and Spectroelectrochemical Properties of Model Compound 92
4.3 Electrochemical Polymerization of Monomers 101
4.4 Optical Properties 116
4.5 Electrochemical Properties of the Polymer Films 118
4.6 Spectroelectrochemical Properties of Polymers 122
4.7 Electrochromic Switching 130
4.8 Electrochromic Devices 136
CHAPTER 5 139
CONCLUSIONS 139
REFERENCES 140

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