星型液晶材料及磷光發光材料之合成與研究

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姓名

王月汝(Yueh-Ju Wang) 查詢紙本館藏

畢業系所

化學學系

論文名稱

星型液晶材料及磷光發光材料之合成與研究
(New star-shaped mesophase & phosphorescence emitting materials: synthesis, mesomorphic behavior, and photophysical properties)

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摘要(中)

第一部分:
設計與合成有機液晶材料，選擇非平面之分子中心(triphenylamine, TPA)，藉由引入適當之分子間作用力如氫鍵、π-π作用力或偶極力使TPA
衍生物具有液晶性質；另外也藉由TPA 的發光、電化學及堆疊等性質，在
引入液晶相後得到同時具有發光、電荷傳遞能力及液晶性質的材料。以熱
差式分析儀(DSC)、偏光顯微鏡(POM)與粉末X 光繞射(XRD)鑑定液晶相
與排列方式，並利用循環伏安法(CV)、吸收與放射光譜(UV-Vis, PL)探討
化合物的電化學與光化學性質。研究結果發現在TPA 衍生物中引入氫鍵及
偶極力可得到具有液晶性質之化合物，而π-π作用力的引入使分子間有較
佳的堆疊但不具液晶相。TPA 衍生物具有良好的氧化還原可逆性，且氮原
子上的取代基類型及側鏈基的根數，對於材料的性質有明顯的影響，藉由
引入適當的分子間作用力而得到具有非結晶性且具有液晶相之TPA 衍生
物，使得材料可應用的溫度範圍更加寬廣，更進一步合成出具有高量子產
率及有永久偶極之液晶相化合物。
第二部分:
研究與合成有機銥金屬磷光材料，藉由合成不同的中心雜環
(oxadiazole 或thiodiazole)配位基與常見之單負價雙牙配位基，我們合成了
一系列具磷光發光性質之銥金屬錯合物。除了改變配位基中心雜環分子之
外，我們並且利用不同的推、拉電子基、共軛系統之長短及改變單負價雙
牙配位基等，進而調整磷光材料之發光光色。將雜環的氧改成硫，其發光
光色會紅移28-68 nm；我們增加或減少分子的共軛程度，可以用來微調錯
合物的LUMO 能階；另外，推拉電子基的加入可同時改變錯合物的
HOMO 及LUMO 能階，利用這三個方向來調變材料的發光光色。我們得到ㄧ系列放光由綠光到紅光的磷光材料，由中間體及最終產物的單晶結構
可確定配位基與銥金屬的配位方式，並利用循環伏安法、吸收與放射光譜
探討化合物的電化學與光化學性質。

摘要(英)

Part I:
In this thesis, a new type of organic mesogenic materials is prepared and studied, in which a non planar structure, triphenylamine (TPA) is applied as core group and weak interaction such as H-bondings and/or π-π interaction was
used to induce the mesogens. Also, their interesting mesomorphic behavior,
optical properties and electrochemical properties resulted from core TPA were
investigated. The phase behavior of these mesogenic compounds was characterized and studied by differential scanning calorimetry, polarized optical
microscopy and powder XRD diffraction. The mesophase observed by all
compounds were found to be side dependent. Compounds appended with one,
two or three side chains exhibited lameller columnar (ColL) phases, and
compounds with four or six side chains formed hexagonal columnar (Colh)
phases. The formation of the mesophase, lamellar or columnar mesophases was
probably induced by H-bonding formed between -CH2NH groups. Introductionof H-bonding and dipole was attributed for the better mesomorphic behavior.
Also π-πinteraction was found important in the formation of the mesophases.
The optical and electrochemical properties was studied by UV-vis,
photoluminescence and cyclic voltammetry (CV). All compounds derived from
TPA showed good reversible redox behavior, and the substituents on the
nitrogen atom and/or the numbers of the terminal alkoxy chains showed an
apparent effect on the physical properties.
Part II:
A new family of Iridium(III) complexes derived from oxadiazole and
thiodiazole derivatives as ligands was prepared and their potential applications
as light emitting materials was also studied. By choosing a variety of electrondonor
and electron withdrawing groups, an increase/decrease in molecular
resonance length or/and changing different monodentate ligand, a quite wide
range of emitting wavelengths observed by these luminescence materials were
obtained. A few single crystal structures of iridium(III) complexes were also
resolved and analyzed. The replacement of oxygen atom by sulfur atom in
chromophore a red shift about 28-68 nm in the emitting wavelength was found.
Both The relative energy on the HOMO and LUMO orbitals was changed by
electron-donor or electron-withdrawing group. On the other hand, the LUMO
can also be adjusted by resonance lengths. By using those methods mentioned
above, red emitting and green emitting materials were prepared in this thesis.
The physical properties studied by UV-Vis, photoluminescence and cyclic
voltammetry were also studied and discussed.

關鍵字(中)

★ 發光
★ 液晶

關鍵字(英)

★ emitting material
★ liquid crystal

論文目次

目錄
第一章星型液晶材料之合成與研究 1
第一節緒論 2
1-1 液晶的簡介與應用 3
1-2 相關文獻 5
1-3 研究動機 9
第二節實驗部分 10
2-1 實驗藥品 10
2-2 儀器設備 11
2-3 實驗流程 18
2-4合成步驟 21
第三節結果與討論 46
3-1 化合物命名 46
3-2 化合物的合成與鑑定 46
3-2-1 Schiff Base and Reduction Reactions 47
3-2-2 Aldo Condensation Reactions 47
3-2-3 Witting Reactions 47
3-2-4 化合物的鑑定 48
3-3 液晶相的探討 48
3-3-1 光學紋理之探討 48
3-3-2 熱分析結果之探討 50
3-3-3 變溫粉末繞射之探討 58
3-3-4 分子體積的演算 62
3-4 化合物的相關物性探討 63
3-4-1 光化學性質之探討 63
3-4-2 電化學性質之探討 70
第四節結論 75
參考文獻 77
第二章磷光發光材料之合成與研究 80
第一節緒論 81
1-1 有機電激發光二極體之簡介 81
1-2 螢光與磷光 84
1-3 有機電機發光二極體材料 86
1-4 磷光材料發展 87
1-5 研究動機 92
第二節實驗部分 94
2-1 實驗流程 94
2-2 合成步驟 96
第三節結果與討論 107
3-1 化合物命名 107
3-2 化合物的合成與鑑定 108
3-2-1 Orthometalation Reactions 108
3-2-2 化合物的鑑定 108
3-3 X-ray結構鑑定 108
3-4 物理光學性質探討 124
3-4-1 吸收光譜(UV-Vis) 124
3-4-2 放光光譜(PL) 130
3-5 電化學性質探討 134
第四節結論 139
參考文獻 141

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指導教授

賴重光(Chung K. Lai)

審核日期

2007-7-23

推文