臺灣博碩士論文加值系統

A部份摘要：藉著本實驗室研究無機液晶多年的基礎，我們試著整合兩個液晶的次領域，無機液晶和香蕉形液晶，來獲取新的物質特性。令人驚喜地，我們不但得到B7相的無機液晶，同時單晶繞射、粉末繞射和光電測試的實驗結果，也給了我們許多証據來解答過去B7相文獻中的疑問；進一步揭開B7相神秘面紗。

B部份摘要：我們成功地利用便利的合成步驟取得烷氧碳鏈取代的benzil，大大提升了過去無法達到的高合成效率，並利用我們合成出的benzil製造良好發光性質的quinoxaline液晶和鋅錯合物的無機液晶。高量子產率的液晶具有製造極化放光和高載子效率材料的潛力。

Abstract of series A: With the foundation of works at metallomesogens, we attempt on integrating these two sub-fields of liquid crystals, metal- containing and the fashion banana-shaped mesogens to achieve the new realm. Surprisingly, conspicuous fruitful results come into view. The first single crystal of a homologue molecule exhibiting B7 mesophase has been made. Combining the powder X-ray data and electro-optical measurements, astounding structural information are obtainted and suggest that previous investigations could be associated and there are proper answers to the doubts.

Abstract of series B: We successfully synthesized alkoxy-substituted benzils, which were used to prepare quinoxalines and zinc (II) bis(quinoxalinol). Our results indicated that the products showed discotic mesophases, and the good quantum yields can give the potential of polarized luminescence and high carrier mobility.

中文摘要.......................I
英文摘要.......................II
謝誌...........................III
目錄...........................IV
圖目錄.........................VII
表目錄.........................X
A部份第一章 緒論...............1
A1-1 前言......................2
A1-2 香蕉形液晶................3
A1-3研究之動機.................16
A1-4 參考文獻..................17
A部分第二章 實驗...............19
A2-1 實驗藥品..................20
A2-2 儀器設備..................22
A2-3 A系列實驗流程.............27
A2-4 實驗步驟..................28
A2-4-1 4-Alkoxyacetophenones之合成.............28
A2-4-2 4’-n-Alkoxy-2-hydroxyacrylophenones之合成.............................................28
A2-4-3 N,N’-Bis[1-(4’-alkoxy-phenyl)-3-oxopropenyl]-2,2-dimethyl-
propylenediamines之合成........................31
A2-4-4 N,N’-Bis[1-(4’-alkoxyphenyl)-3-oxopropenyl]-2,2-dimethyl- propylenediamine palladium(II) complexes之合成..................35
A2-4-5 N,N’-Bis[1-(4’-alkoxyphenyl)-3-oxopropenyl]-2,2-dimethyl- propylenediamine nickel(II) complexes之合成.....................38

A2-4-6 N,N’-Bis[1-(4’-alkoxyphenyl)-3-oxopropenyl]-2,2-dimethyl- propylenediamine copper(II) complexes之合成.....................39
A2-4-7 N,N’-Bis[1-(4’-alkoxy-phenyl)-3-oxopropenyl]-2,2-dimethyl-
propylenediamines之合成.............................................41
A2-4-8 3-{1-Ethyl-3-[3-hydroxy-3-(4-alkoxy- phenyl)-allylidene- amino]-propylimino}-1-(4-alkoxy-phenyl)-propen-1-ol palladium(II) complexes之合成…...........................................43
A2-4-9 3-{1-Ethyl-3-[3-hydroxy-3-(4-alkoxy- phenyl)-allylidene- amino]-propylimino}-1-(4-alkoxy-phenyl)-propen-1-ol nickel(II) complexes之合成.............................................44
A2-4-10 3-{1-Ethyl-3-[3-hydroxy-3-(4-alkoxy- phenyl)-allylidene- amino]-propylimino}-1-(4-alkoxy-phenyl)-propen-1-ol copper(II) complexes之合成...........................................45
A部分第三章 實驗結果與討論.....................47
A3-1 化合物合成反應機制之討論..................48
A3-2 液晶相及相溫度範圍鑑定....................52
A3-3 光電測試..................................58
A3-4 X-ray粉末繞射.............................60
A3-5 X-ray單晶繞射.............................64
A3-6 結論......................................68
A3-7 參考文獻..................................69
B部份第一章 緒論...............................70
B1-1 前言......................................71
B1-2具先進技術應用潛力的液晶材料...............72
B1-3研究之動機.................................84
B1-4 參考文獻..................................85
B部分第二章 實驗...............................87
B2-1 實驗藥品..................................88
B2-2 儀器設備..................................89
B2-3 B系列實驗流程.............................91
B2-4 實驗步驟..................................92
B2-4-1 1,2-bis(3,4-dialkoxyphenyl)-1,2-ethanedione之合成..............................92
B2-4-2 2,3,7,8-Tetrakis-(3,4-dialkoxy-phenyl)-pyrazino[2,3-g]quinox- aline之合成.............................................94
B2-4-3 2,3,2’,3’-Tetrakis-(3,4-diAlkoxyphenyl)-[6,6’]biguinoxalinyl之合成....................97
B2-4-4 2,3-Bis-(3,4-dialkoxy-phenyl)-quinoxalin-5-ol之合成....................................100
B2-4-5 Zinc(II) 2,3-bis-(3,4-dialkoxy-phenyl)-quinoxalin-5-olate之合成......................102
B部分第三章 實驗結果與討論....................104
B3-1 化合物合成反應機制之討論.................105
B3-2 液晶相及相溫度範圍鑑定...................108
B3-3 物理性質探討.............................115
B3-4 結論.....................................123
B3-5 參考文獻.................................124
附圖..........................................126



圖目錄
圖A1之一、B1相香蕉形液晶........................3
圖A1之二、具B2相之分子..........................5
圖A1之三、Link等人在1997所提出的香蕉形液晶模形..6
圖A1之四、B2相分子的介電吸收測試................7
圖A1之五、B2相的switching current response......8
圖A1之六、香蕉形分子在立體空間中的結構形式......9
圖A1之七、B3和B4相的X-ray圖譜..................10
圖A1之八、B5相的二維繞射結果...................11
圖A1之九、B6相的二維繞射結果...................12
圖A1之十、文獻中B7相的分子結構.................14
圖A1之十一、B7相偏光紋理圖.....................15
圖A1之十二、發表在Science, 2003, 301, 1204的B7相研究結果.......................................16
圖A2之一、光電測試系統接線圖...................24
圖A2之二、布拉格繞射示意圖.....................26
圖A2之三、A系列的合成步驟......................27
圖A3之一、A系列的合成步驟......................48
圖A3之二、The Williamson ether synthesis.......49
圖A3之三、The Calisen condensation.............50
圖A3之四、A mechanism for imine formation......51
圖A3之五、具有香蕉形液晶相之Pd(J-Cn)鈀金屬錯合物.............................................52
圖A3之六、Pd(J-Cn)的溫度柱狀圖.................56
圖A3之七、Pd(J-C14)在121℃的偏光紋理圖.........57
圖A3之八、Pd(J-C14)的switching current response.......................................58
圖A3之九、Pd(J-Cn)的結構資訊...................64
圖A3之十、Pd(J-Cn)螺旋六角柱液晶相的模型.......67
圖B1之一、OLED發光機制.............................................72
圖B1之二、OLED元件示意圖.......................73
圖B1之三、PPV (poly(p-phenylene vinylene))，第一個PLED.........................................74
圖B1之四、螢光與磷光發光機制...................75
圖B1之四、場效電晶體示意圖.....................77
圖B1之五、太陽能電池的能階圖...................79
圖B1之六、近期文獻中應用在載子傳輸方面的液晶分子.............................................80
圖B1之七、F(MB)10F(EH)2........................82
圖B1之八、利用可光聚合的發光液晶...............82
圖B1之九、應用在雷射旋光nematic液晶的螺旋結構..83
圖B1之十、(Bx-Cn)和(Py-Cn)，兩個有機系列液晶...84
圖B1之十一、Zn(Q-Cn)無機液晶.............................................84
圖B2之一、B系列的合成步驟......................91
圖B3之一、B系列的合成步驟………………….................................106
圖B3之二、A mechanism for Friedel-Crafts reaction…………............107
圖B3之三、B系列的液晶相柱狀圖…………………….....................111
圖B3之四、Bx-C14於84.5℃下之Colr相偏光紋理圖………..……....112
圖B3之五、Py-C14於67℃下之Colh相偏光紋理圖…….……..……..113
圖B3之六、Zn(Q-C14)於108℃下之Colr相偏光紋理圖……....…..113
圖B3之七、Bx-C14及Py-C14的UV吸收光譜….....…………..……115
圖B3之八、Bx-C14及Py-C14的螢光放射光譜……….…………….116
圖B3之九、CV圖………………………...……...................................118
圖B3之十、化合物Bx-C10、Py-C10、Zn(Q-C10)之能階圖………….119
圖B3之十一、TOF技術載子遷移率測量示意圖…………………120
圖B3之十二、文獻中的(Znq2)n寡聚體…………………………122

表目錄
表A2之一、實驗所用之化學藥品……………….….…….…...............20
表A3之一、配位基J-Cn之熱分析數據..……….……..….....................53
表A3之二、錯合物M(J-Cn)之熱分析數據………................................54
表A3之三、錯合物M(K-Cn)之熱分析數據…………....................…55
表A3之四、X-ray data for Pd(J-C10), Pd(J-C12) and Pd(J-C16)….....61
表A3之五、X-ray data for Pd(J-C14) and Pd(J-C18)………………....63
表B2之一、實驗所用之化學藥品…………………..............................88
表B3之一、Bx-Cn之熱分析數據……………………………….......108
表B3之二、Py-Cn之熱分析數據………………….…………..........109
表B3之三、錯合物Zn(Q-Cn)之熱分析數據....…………………........110
表B3之四、X-ray粉末繞射數據….…………………......................…114
表B3之五、Bx-Cn及Py-Cn的螢光最大放射峰及量子產率………...117
表B3之六、化合物之氧化還原電位及HOMO、LUMO能階……….118

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