臺灣博碩士論文加值系統

本篇論文系列一合成設計出含有benzoxazole與benzothiazole衍生物的配位基和金屬錯合物(銅、鈀)，藉由改變側鏈基的長短，討論其液晶之行為，並透過DSC、POM、XRD 等儀器來觀察其液晶在不同溫度下的性質。研究發現，含有benzoxazole衍生物的配位基當其側鏈基長碳鏈數目為8和10時具有N液晶相，側鏈基長碳鏈數目為12、14以及16時具有SmC液晶相；含有benzothiazole衍生物的配位基其側鏈基長碳鏈數目為8同時具有N液晶相以及SmC液晶相。將benzoxazole與benzothiazole衍生物的配位基和金屬配位，並藉由IR光譜確認配位基確實與金屬配位。POM發現benzoxazole衍生物之(銅、鈀)金屬錯合物皆不具任何液晶相。benzothiazole衍生物之銅金屬錯合物亦不具任何液晶相。benzothiazole衍生物之鈀金屬錯合物側鏈基長碳鏈數目為8, 10, 12, 14, 16時皆具有SmC液晶相。
系列二合成設計出含有benzothiazole衍生物，置換苯環4位置上的取代基，探討取代基對液晶行為之影響，研究中發現末端若無任何取代基，則無法產生液晶性質；若末端取代基接上推電子基，則產生nematic液晶相；若末端取代基接上拉電子基，則產生SmA液晶相。並利用取代基常數、dipole moment等性質說明液晶相形成的原因。

In the first series synthesis, characterization and mesomorphic behavior of a series of benzoxazole and benzothiazole derivatives 2 and their complexes 1 (M = Pd, Cu) are described. The mesomorphic properties were investigated using polarized optical microscopy (POM), differential scanning calorimetry (DSC), powder X-ray diffraction (XRD). The results indicated that ligands based on benzoxazole with carbon length of n = 8, 10 showed nematic (N) mesophase; with carbon length of n = 12, 14, 16 showed smetic C (SmC) mesophase. All palladium (II) and copper (II) complexes of benzoxazole derivatives were not mesogenic. Ligands based on benzothiazole with carbon length of n = 8 showed nematic (N) and smetic C (SmC) mesophase; with carbon length of n = 10, 12, 14, 16 showed smetic C (SmC) mesophase. Copper (II) complexes of benzothiazole derivatives were not mesogenic. However, palladium (II) comlexes of benzothiazole derivatives with carbon length of n = 8, 10, 12, 14, 16 showed smetic C (SmC) mesophase.
In the second series, the effect of substituent group on the formation of the mesophases were investigated by Hammett constant, and dipole moment. A SmA phase was observed for derivatives with a strong electrondrawing substituent, and a N phase was observed for the derivative with an electrondonating substituent.

中文摘要 ................................................. V
Abstract ............................................... VI
謝誌 ................................................... VII
目錄 .................................................. VIII
圖目錄 .................................................. XII
附圖目錄 ................................................ XXI
第一章 緒論................................................ 1
1-1液晶簡介 ............................................... 2
1-2液晶組成條件和物理特性 .................................... 5
1-3 液晶分類 ............................................. 11
1-3-1依液晶相形成方式分類 .................................. 13
1-3-2以液晶分子之形狀分類 .................................. 14
1-4 不同取代基對液晶材料的影響 .............................. 17
1-5 無機液晶 ............................................. 21
1-5-1無機液晶之特性 ....................................... 22
1-5-2以中心金屬配位之方式去探討無機液晶 ....................... 24
1-6 研究動機 ............................................. 29
第二章 實驗部分 ........................................... 32
2-1 實驗藥品 ............................................. 33
2-2 儀器設備 ............................................. 35
2-3 實驗流程 ............................................. 38
2-3-1 系列一之實驗流程 ..................................... 38
2-3-2 系列二之實驗流程 ..................................... 39
2-4 實驗步驟 ............................................. 40
2-4-1 系列一之合成 ........................................ 40
2-4-2 系列二之合成 ........................................ 64
第三章 結果與討論 .......................................... 75
3-1 配位基與錯合物結構與代號 ................................ 76
3-2 系列一配位基2a及2b之探討 ............................... 77
3-2-1 系列一配位基2a及2b之元素分析及質譜分析 .................. 77
3-2-2 系列一配位基2a及2b之偏光紋理圖 ........................ 78
3-2-3系列一配位基2a及2b之DSC數據討論 ........................ 82
3-2-4 類似結構之熱分析結果比較 .............................. 85
3-2-5系列一配位基2a及2b之變溫X-ray繞射討論 ................... 87
3-2-6 系列一配位基2b之單晶結構與排列 ......................... 98
3-2-7 系列一配位基2a、2b之分子排列探討 ...................... 103
3-2-8 系列一配位基2a、2b以及2a’之液態光學性質探討 ............ 105
3-3 系列一Cu錯合物1a-Cu及1b-Cu之討論 ...................... 109
3-3-1 系列一錯合物1a-Cu及1b-Cu之偏光紋理圖 ................. 109
3-3-2系列一Cu錯合物1a-Cu及1b-Cu之DSC數據討論 ............... 112
3-3-3 系列一Pd錯合物1a-Pd及1b-Pd之討論: ................... 113
3-3-4 系列一錯合物1b-Pd之元素分析及質譜分析 .................. 113
3-3-5 系列一錯合物1a-Pd及1b-Pd之偏光紋理圖 ................. 114
3-3-6系列一Pd錯合物1a-Pd及1b-Pd之DSC數據討論 ............... 117
3-3-7系列一錯合物1b-Pd之變溫X-ray繞射討論 .................. 119
3-3-8 配位基2a、2b與金屬錯合物1a-Cu、1a-Pd、1b-Cu以及1b-Pd之IR光譜數據討論 ................................................ 122
3-4 系列二取代基效應化合物3c之探討 .......................... 125
3-4-1 系列二取代基效應化合物3c之元素分析及質譜分析 ............ 125
3-4-2系列二化合物3c之偏光紋理圖 ............................ 126
3-4-3系列二化合物3c之DSC數據與取代基效應探討 ................. 129
3-4-4 單晶結構與排列 ..................................... 139
3-4-5 系列二化合物3c之UV-Vis吸收光譜探討 ................... 143
3-5結論 ................................................ 145
3-5-1 系列一結論 ........................................ 145
3-5-2 系列二結論 ........................................ 146
參考文獻 ................................................ 147
附圖 .................................................... 15

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