含pyrazole, 1,3,4 - thiadiazole雜環以及BF2-chelated 結構之桿狀液晶性質探討

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許圓君(Yuan-Chun Hsu) 查詢紙本館藏

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論文名稱

含pyrazole, 1,3,4 - thiadiazole雜環以及BF2-chelated 結構之桿狀液晶性質探討

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摘要(中)

本篇論文主要分為兩個系列，在系列一中成功合成以pyrazole及1,3,4-thiadiazole雜環為中心硬核之1a-b與2為配位基，與boron difluoride (BF2) 形成錯合物1a-BF2、1b-BF2及2-BF2。藉由引入以雜環系統為主結構之配位基再接上boron difluoride (BF2) 成為硼錯合物來觀察其對液晶形為表現的影響。研究發現中心雜環為pyrazole的化合物1a-b具有SmA或SmC的桿狀液晶相而將雜環換成1,3,4-thiadiazole的化合物2則具有N、SmA或SmC相且液晶相範圍較1a-b廣，再來螯合上BF2的化合物1a-BF2、1b-BF2則無液晶相生成，而化合物2-BF2具有SmA相。從培養出的化合物1a (n = 5)、2 (n = 6) 以及2 (n = 10) 單晶探討分子排列以及其分子間之作用力並以XRD實驗結果推論其在液晶相之排列情形。化合物1a-b、2以及2-BF2 (長碳鏈總碳數相同) 以UV可見光吸收光譜以及螢光放光光譜來探討其光學性質，由結果得知化合物2-BF2的放光波長較2的波長藍移且量子產率也較高。另外，化合物2受excited state intramolecular proton transfer (ESIPT) effect 影響，其Stokes shift大於化合物2-BF2。
系列二成功合成出以淳洋學長之benzothiazole結構，化合物3為中心雜環作為配位基並與BF2進行螯合形成硼錯合物3-BF2 (n = 8, 10, 12)，經POM與XRD粉末繞射實驗之結果判斷3-BF2 (n = 8) 具有N相以及SmC相，而3-BF2 (n = 10-12) 則具有SmC相桿狀液晶。從培養出的化合物3-BF2單晶與淳洋學長培養的化合物3單晶比較並探討分子排列以及其分子間之作用力。另外化合物3 (n = 12)以及3-BF2 (n = 12) 以UV可見光吸收光譜以及螢光放光光譜來探討其光學性質，由結果得知化合物3-BF2的吸放光波長較3的波長紅移且量子產率也較高。

摘要(英)

Nowadays more and more liquid-crystalline compounds containing five-membered hetrocycles are the subject of many investigations. These heterocyclic structures generally incorporated of such electronegative atoms (S, O or N atom) often resulted in a reduced or lowering symmetry for the overall molecules or/and a stronger polar induction. Quite a few examples, including pyrazoles, isoxazoles, 1,3,4-oxadiazoles, 1,3,4-thiadiazoles and others have been prepared and investigated in our group. Most of them formed smectic phases whereas, only a few of them exhibited columnar phases.
Additionally, complexes containing boron difluoride (BF2) have been paid much attention in the past few years. Many of boron difluoride complexes have been investigated as fluorescent materials, thus showing potential applications in many fields; such as biological imaging, molecular probes, electroluminescent devices, photosensitizers and others. However, they seldom reported as mesogenic applcations.
In series I, a new series of symmetry pyrazole or 1,3,4-thiadiazole compounds 1a-b and 2, and mono-(boron difluoride) complexes 1a-BF2, 1b-BF2 and 2-BF2 derived from 1a-b and 2 was synthesized and their mesomorphic and optical properties were also investigated. The single crystals of mesogenic 1a (n = 5), 2 (n = 6), 2 (n = 10) were obtained, and its single crystal and molecular structures were resolved. The results suggested that compounds 1a-b, 2 and 2-BF2 exhibited enantiotropic smectic mesophases and 1a-BF2, 1b-BF2 were nonmesogenic. The luminescent emission showed that ligand 2 exhibited a larger Stokes shift than complexes 2-BF2 beacause of excited state intramolecular proton transfer (ESIPT) effect.
In series II, a new series of mono-(boron difluoride) complexes 3-BF2 derived from substituted benzothiazole Schiff base 3 were reported, and their mesomorphic and optical properties were also investigated. The single crystals of mesogenic boron complexes 3-BF2 (n = 8) was obtained, and its single crystal and molecular structures were resolved. The results suggested that mono-(boron difluoride) complexes 3-BF2 exhibited enantiotropic smectic mesophases. The luminescent emission showed that in the excited state, the position of the maximum appears to be dependent on the chelation of BF2 as visible red shifts from 524 nm to 565 nm of the emission bands are detected in compounds 3 and 3-BF2.

關鍵字(中)

★ 液晶

關鍵字(英)

★ mesogen
★ liquid crystal

論文目次

中文摘要 I
Abstract III
謝誌 V
目錄 VI
圖目錄 IX
表目錄 XIV
第一章緒論 1
1-1液晶簡介 2
1-2 液晶分子的基礎架構 3
1-3 液晶分子間作用力 3
1-4 液晶分類 4
1-4-1向列型液晶 6
1-4-2層列型液晶 6
1-4-3盤狀液晶 7
1-5 五員雜環簡介 8
1-6 Boron difluoride complexe簡介 10
1-7研究動機 12
1-7-1系列一之研究動機 12
1-7-2系列二之研究動機 13
第二章實驗步驟 15
2-1實驗藥品 16
2-2儀器設備 17
2-3實驗流程 20
2-3-1系列一之實驗流程 20
2-3-2系列二之實驗流程 21
2-4實驗步驟 22
2-4-1系列一之合成步驟 22
2-4-2系列二之合成步驟 35
第三章結果與討論 43
3-1結構與代號 44
3-2系列一化合物之探討 45
3-2-1系列一化合物之偏光紋理圖 (POM) 45
3-2-2系列一化合物 1a、1b、2之熱微差掃描分析 (DSC) 51
3-2-3類似結構之熱分析比較 56
3-2-4系列一 1a、1b、2與2-BF2之變溫X-ray繞射討論 58
3-2-5系列一化合物 1a之單晶與分子排列探討 65
3-2-6系列一化合物 2 (n = 6, 10) 之單晶與分子排列探討 73
3-2-7系列一1a、1b、2以及2-BF2之液態光學性質探討 83
3-3系列二化合物之探討 86
3-3-1系列二化合物之偏光紋理圖 (POM) 86
3-3-2系列二化合物 3及3-BF2之熱微差掃描分析 (DSC) 88
3-3-3系列二化合物3及3-BF2之變溫X-ray繞射討論 91
3-3-4系列二化合物3及3-BF2之單晶與分子排列探討 93
3-3-5系列二3以及3-BF2之液態光學性質探討 102
第四章結論 104
4-1系列一之結論 105
4-2系列二之結論 106
參考文獻 107
附圖 113
附表 139

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指導教授

賴重光(Chung-Kuang Lai)

審核日期

2018-7-10

推文