萘環與異雜環對液晶性質影響之探討

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文斐(Fei Wen) 查詢紙本館藏

畢業系所

化學學系

論文名稱

萘環與異雜環對液晶性質影響之探討

相關論文

★ 具有benzoxazole結構之無機液晶材料	★ 以1,3,4-thiadiazole為架構之不對稱無機液晶材料
★ 新穎香蕉形液晶及對稱含萘環之液晶分子	★ 香蕉形無機液晶
★ 具有benzoxazole結構之有機及無機液晶材料	★ 以1,3,4-thiadiazole為架構之無機盤狀液晶材料
★ 以benzoxazole為架構之無機桿狀液晶	★ 具有Quinoxaline結構之雙金屬無機液晶材料
★ 星型液晶材料及磷光發光材料之合成與研究	★ 含pyrazole及isoxazole之有機桿狀液晶
★ 矽咔哚與矽螺旋雙笏物質之放光性質研究	★ 具有Benzobisthiazoles和Benzobisoxazoles結構之盤狀液晶材料
★ 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)

由於放光材料於分子辨識、螢光探針、顯微鏡成相、有機發光二極體 (OLED)等現代科技中被廣泛應用，故放光範圍寬廣之發光材料於近期吸引科學家們的研究與討論。液晶材料具有良好的自組裝特性，其誘導分子間無缺陷排列的能力與高電荷遷移率皆可進而提升裝置之效能。開發同時具有液晶與發光特性之材料則是目前的一大挑戰。
本研究延伸實驗室先前所研究之結構，保留分子同時含有五員雜環與 β-diketonate 之設計，以及含有相異雙五員雜環之設計，將化合物 1a-b、 3a-c 其中一側之苯環置換成萘環，製備化合物 2a-b、4a-c，藉此延長分子內的共軛系統、增加分子結構之不對稱性及分子間作用力，並藉由偏光顯微鏡、微差式掃描熱分析儀與 X-ray 繞射之鑑定得知，含有萘環之化合物 2a-b、4a-c 成功誘導出較寬廣之液晶相範圍。此外，將化合物 1a-b、2a-b 與二氟化硼進行配位，藉由硼原子缺乏 p 軌域電子的特性，延長其錯合物分子內之共軛並降低分子的 LUMO 軌域，成功開發放光紅移、較大 stokes shift 之化合物 1a-BF2、1b-BF2、2a-BF2、2b-BF2。本研究亦將化合物 1a- b、2a-b 與 Cu 進行配位，引入重原子效應，希望開發高量子產率之磷光液晶材料，此系列化合物 1a-Cu、1b-Cu、2a-Cu、2b-Cu 雖具有液晶性質，但不具有良好之熱穩定性，其熱裂解溫度低於成清點溫度，故未進行光物理性質之測試。

摘要(英)

In recent years, emission materials are especially interesting because the wide range of applications in advanced technologies such as molecular recognition, fluorescence probes, microscopy imaging, and organic light-emitting diodes (OLEDs). Liquid crystals are also interest in research, because its properties of orientational ordering and molecular self-organization. These materials provided charge carrier mobility to improve device performance. Therefore, exploiting the luminesecent mesogens actract lots of discussion.
In this work, five-membered heterocyclic ring derivatives 2a-b, 4a-c and their borondifluoride complexes 1a-BF2, 1b-BF2, 2a-BF2, 2b-BF2 and coper complexes 1a-Cu, 1b-Cu, 2a-Cu, 2b-Cu were prepared and investigated. All compounds were characterized by 1H and 13C NMR spectroscopes, elementary analysis. Their mesomorphic behavior was studied by polarized optical microscope, differential scanning calorimeter and X-ray diffraction. All compounds exhibited liquid crystal phases except borondifluoride complexes. Futhermore, compounds 2a-b, 4a-c with five-membered heterocyclic ring and naphthalene have wider mesophases, owing to the increasing of structure asymmetry and intermoluce interaction. Optical property was investigated by UV/Vis and photoluminescence spectroscopy. Because of the donor-acceptor effect, their BF2 complexes have emissions of near-infrared wavelengths.

關鍵字(中)

★ 液晶
★ 異雜環
★ 萘環

關鍵字(英)

★ liquid crystal
★ heterocyclic ring
★ naphthalene

論文目次

第一章、緒論 ............................................................................................................................ 1
1-1 液晶的起源 .....................................................................................................................2
1-2 液晶的性質.......................................................................................................................2
1-2-1 液晶的簡介...........................................................................................................................2 1-2-2 液晶的分類...........................................................................................................................3 1-2-3 液晶分子的基礎架構...........................................................................................................5
1-3 液晶分子的結構設計.......................................................................................................6 1-3-1 五員雜環...............................................................................................................................6 1-3-2 二氟化硼(BF2)簡介..............................................................................................................7 1-3-3 銅...........................................................................................................................................8
1-4 研究動機...........................................................................................................................8
第二章、實驗與合成 .............................................................................................................. 11 2-1 儀器設備............................................................................................................................ 12 2-2 實驗藥品............................................................................................................................ 16 2-3 實驗簡介...........................................................................................................................16 2-4 合成步驟...........................................................................................................................17 第三章、結果與討論 .............................................................................................................. 46
3-1 核磁共振儀(NMR)與電子順磁共振儀(EPR)光譜鑑定 ................................................. 47
3-1-1 NMR 光譜討論.................................................................................................................... 47
3-1-2 EPR 光譜討論...................................................................................................................... 48
3-2 偏光紋理圖.......................................................................................................................55
3-3 熱微差掃描分析儀(DSC)數據表....................................................................................58
3-4 X-ray 繞射儀分析及分子間作用力模擬 ......................................................................... 64
3-4-1 化合物2a-b之X-ray光譜及其分子排列模擬................................................................64 3-4-2 化合物 4a-c 之 X-ray 光譜及其分子排列模擬................................................................. 69 3-4-3 銅錯合物 2a-Cu、2b-Cu 之 X-ray 光譜及其分子排列模擬........................................... 70
3-5 熱重分析............................................................................................................................ 76 iii
3-6 光物理性質探討...............................................................................................................78 第四章、結論 .......................................................................................................................... 82 第五章、曾製備之結構 .......................................................................................................... 85 參考文獻 ................................................................................................................................ 101 附錄 ........................................................................................................................................ 104

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指導教授

賴重光

審核日期

2021-7-21

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