以對稱Pyrazoles架構之無機液晶材料

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姓名

林慧芸(Huei-Yun Lin) 查詢紙本館藏

畢業系所

化學學系

論文名稱

以對稱Pyrazoles架構之無機液晶材料
(New Bimetallomesogens Derived from Symmetric Pyrazoles.)

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★ 含 Benzoxazole 之對稱二聚物其奇偶效應的探討	★ 以電腦模擬研究香蕉型液晶元的分子交互作用力
★ 極性取代基對於彎曲型液晶分子的影響	★ 由彎曲型分子形成盤狀液晶之探討

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摘要(中)

本篇論文主要包含具有pyrazole結構液晶。所有化合物經由1H-NMR、13C-NMR與元素分析以鑑定其結構及純度，液晶相性質則是利用偏光顯微鏡(POM)來觀測相種類及熱微差掃描分析儀(DSC)測量相變化時之溫度與熱焓值，最後以變溫粉末X光繞射儀(XRD)確認相的種類。
我們成功的合成出兩個系列具pyrazole結構分子。配位基之中心苯環上具有間位取代Mpn時，不具液晶相，然而產生銅錯合物Cu-mpn時，則具有SmA相。特別的是，若對位取代的化合物Ppn，則呈現SmC/SmA液晶相，產生銅錯合物Cu-ppn時，化合物具有SmA/SmC 相。
除此之外，我們亦合成了中心苯環上具有1, 3, 5取代之 Tp8與2Tp12，其不具有液晶相。然而，2Tp12之前驅物，2Tk12，卻具有ColL相。

摘要(英)

In this thesis, we report the synthesis, characterization and mesomorphic properties of five novel series of new mesogenic derivates based on pyrazole structures. All compounds were characterized by 1H, 13C-NMR spectroscopy and elemental analysis. The phase behavior of these mesogenic compounds was characterized and studied by differential scanning calorimeter (DSC) and polarization optical microscope.
In this work, two series of pyrazole derivatives as coordinating ligands and their copper (II) complexes Cu-mpn and Cu-ppn were prepared and their mesomorphic properties investigated. All pyrazoles Mpn with a meta-substituted benzene were not mesogenic, however, all copper (II) complexes Cu-mpn formed smectic A phases. Interestingly, another series of pyrazoles Ppn with a para-substituted benzene and their copper (II) complexes Cu-ppn exhibited smectic phases.
In addition, we designed and characterized a series of organic molecule Tp8 and 2Tp12 derived from pyrazole with a 1,3,5-substituted benzene, and they didn’t exhibit mesophase. However, their precursor, 2Tk12, exhibited ColL phase.

關鍵字(中)

★ 雙金屬
★ 液晶
★ 無機液晶

關鍵字(英)

★ bimetallomesogen
★ pyrazole
★ liquid crystal

論文目次

摘要.............................................................IV
Abstract.........................................................V
謝誌.............................................................VI
目錄...........................................................VIII
圖目錄........................................................XII
表目錄....................................................XVIII
第一章緒論..................................................1
1-1液晶的起源及簡介..................................2
1-2液晶的構造與物理性質..........................3
1-3液晶的分類............................................13
1-3-1以液晶相形成之方式分類.................14
1-3-2以液晶分子之形狀分類 .....................15
1-3-2-1桿狀 (rod like) 液晶...........................15
1-3-2-2柱狀(columnar-like)液晶....................16
1-3-3以是否含有金屬分類.........................19
1-4液晶之性質............................................19
1-5無機液晶之特性....................................22
1-6研究動機................................................26
1-6-1系列一與系列二研究動機.................26
1-6-2系列三與系列四研究動機.................28
1-6-3 系列五之研究動機............................30
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系列一與二之實驗流程 .....................38
2-3-2系列三與四之實驗流程 .....................39
2-3-3系列五之實驗流程.............................40
2-4實驗步驟................................................41
2-4-1系列一與二之合成.............................41
2-4-2 系列三與四之合成............................48
2-4-3 系列五之合成....................................53
第三章結果與討論...................................59
3-1化合物代號對照表................................60
3-2 系列一之化合物 Mpn...........................61
3-2-1 化合物之結構鑑定............................61
3-3-1-1 NMR鑑定 ........................................61
3-3-1-2 元素分析 ( EA ) 之鑑定.................64
3-2-2液晶相之鑑定與探討........................65
3-3-2-1 DSC 數據探討................................65
3-2-3 單晶結構...........................................67
3-2-4 powder X-ray......................................75
3-3 系列二之化合物Cu-mpn......................77
3-3-1 元素分析 ( EA ) 之鑑定....................77
3-3-2液晶相之鑑定與探討........................77
3-3-2-1 偏光紋理圖....................................78
3-3-2-2 DSC 數據探討...............................79
3-3-3 powder-XRD.......................................80
3-3-4 Cu-mpn可能之配位方式...................80
3-4 系列三之化合物Ppn............................84
3-4-1元素分析 ( EA ) 之鑑定.....................84
3-4-2液晶相之鑑定與探討........................84
3-4-2-1 偏光紋理圖....................................85
3-4-2-2 DSC 數據探討................................87
3-4-3單晶結構............................................89
3-4-4 powder X-ray......................................97
3-4-5 Mpn與Ppn之討論............................104
3-5 系列四之化合物Cu-ppn.....................109
3-5-1 元素分析 ( EA ) 之鑑定..................109
3-5-2液晶相之鑑定與探討......................110
3-5-2-1 偏光紋理圖..................................110
3-5-2-2 DSC 數據探討..............................113
3-5-3 powder-XRD.....................................114
3-5-4 Cu-ppn可能之配位方式..................116
3-6 系列五之化合物................................120
3-6-1元素分析 ( EA ) 之鑑定...................120
3-6-2液晶相之鑑定與探討......................121
3-6-2-1 偏光紋理圖..................................121
3-6-2-2 DSC 數據探討..............................121
3-6-3 powder-XRD.....................................122
3-7結論.....................................................130
參考文獻..................................................131
附圖..........................................................134

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指導教授

賴重光(Chung-Kung Lai)

審核日期

2009-7-24

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