臺灣博碩士論文加值系統

系列一：設計並合成以bis-(1,3,4-thiadiazole)為主結構之配位基，再接上 PdCl2 或 PdBr2 成為金屬液晶錯合物。利用熱差式分析儀(DSC)、偏光顯微鏡(POM)及粉末 X 光繞射(XRD)鑑定其結構，發現液晶相與側鏈基數目、碳數、金屬鍵結方式與立體障礙都會影響液晶相之範圍。由於 Thiadiazole 的配位基發藍光，有潛力成為發光材料，因此除了液晶行為的探討，我們更進一步利用 UV-Vis 可見光譜、 PL 放射光譜研究其光譜及量子產率。

系列二：系列一之延伸，在配位基中加入 OH 官能基，試圖利用OH官能基與金屬的不同配位方式，產生新的液晶相。由 FT-IR及 NMR 實驗確認配位基中存在著氫鍵，並一步研究 ligand中氫鍵對液晶相之影響，與 PL 光譜的 excited state intramolecular proton transfer(ESIPT) 現象。此系列的金屬鍵結方式與系列一不同，但同樣皆為Colh的盤狀排列，因此我們希望藉由體積量測方法找出鍵結方式對液晶分子排列的影響，並試圖找出其排列方式與規則度。

In the first series, the preparation, characterization and mesomorphic properties of palladium chloride and palladium bromide complexes derived from bis-(1,3,4-thiadiazole) derivatives are described. These compounds with a different number of alkoxy side chain exhibited various mesophases, which were studied and investigated by differential scanning calorimeter (DSC), polarized optical microscopy (POM) and powder X-ray diffraction (XRD). The formation of mesophases was found to be sensitive to the number of the alkoxy side chain, carbon length of the side chains, stereo geometry, and the coordination of metal centers. As light emittng materials, the physical properties by UV-Vis spectrophotometer, and photoluminescence (PL) were also studied and discussed.

In the second series, a new type of metallomesogenic complexes structurally similar to the first series with a OH group added was prepared ane studied. Theses metal complexes were coordinated in different geometries from the first series. All compounds in the series existing intramolecular hydrogen bond and an ESIPT behavior, were investigated by FT-IR and UV-PL. In addition, in order to better understand the molecular arrangement in columnar mesophases, the molecular volume dilatomery and other parameters were also measured and discussed.

中文摘要……………………………………………………………………………I
英文摘要……………………………………………………………………………Ⅱ
謝誌…………………………………………………………………………………Ⅲ
目錄…………………………………………………………………………………Ⅳ
圖目錄……………………………………………………………………………ⅤII
表錄………………………………………………………………………………ⅩⅠ
第一章 緒論
1-1 前言……………………………………………………………………………2
1-2 液晶之起源及簡介……………………………………………………………3
1-3液晶相形成之要件……………………………………………………………5
1-4液晶分子中氫鍵之鑑定方式…………………………………………………11
1-5液晶的分類……………………………………………………………………14
1-6 研究動機………………………………………………………………………19
第二章 實驗部份
2-1 實驗藥品………………………………………………………………………21
2-2 儀器設備………………………………………………………………………23
2-3 實驗流程………………………………………………………………………27
2-3-1 化合物結構與相對應代號一覽表…………………………………………27
2-3-2 系列一合成流程……………………………………………………………29
2-3-3 系列二之一合成流程………………………………………………………30
2-3-4 系列二之二合成流程………………………………………………………31
2-4 實驗步驟……...……………………………………………………………32
第三章 實驗結果與討論
3-1 系列一、系列二化合物之結構鑑定………………………………………52
3-1-1 元素分析與質譜分析……………………………………………………52
3-1-2 3a 與3b 之電子順磁共振(EPR)圖譜……………………………………55
3-2 單晶結構……………………………………………………………………56
3-2-1 錯合物單晶數據…………………………………………………………56
3-2-1-1 錯合物1a(n = 6)與溫長榮學長單晶(1a’)數據之比較……………56
3-2-1-2 錯合物3a(n = 1)之單晶數據…………………………………………64
3-2-2 配位基單晶………………………………………………………………69
3-2-2-1 模擬配位基2a(n = 1) ………………………………………………69
3-2-2-2 配位基2c(n = 8)單晶結構……………………………………………70
3-2-2-3 政宗學長配位基(4c’)單晶數據……………………………………72
3-3 熱分析數據與偏光紋理圖…………………………………………………75
3-3-1 配位基2a ~ 2c 之 DSC 數據與偏光紋理圖.…………………………75
3-3-2 錯合物 1a~1f 之 DSC 數據與偏光紋理圖……………………………79
3-3-3 系列二 4a~4c 之 DSC 數據與偏光紋理圖……………………………87
3-3-4 系列二 3a~3d 之 DSC 數據與偏光紋理圖……………………………88
3-3-5 系列三6a 之 DSC 數據與偏光紋理圖…………………………………92
3-3-6 系列三5a 之 DSC 數據…………………………………………………93
3-4 核磁共振之氫鍵研究………………………………………………………95
3-4-1 液態 NMR 實驗……………………………………………………………95
3-4-2 固態 NMR 實驗……………………………………………………………98
3-5 變溫紅外線光譜法…………………………………………………………99
3-6 配位基分子之光物理性質探討……………………………………………101
3-6-1 配位基4a與4c之光學探討(ESIPT現象) ………………………………104
3-6-2 製膜UV-PL…………………………………………………………………105
3-7 X-ray Diffraction 數據整理…....……………………………………107
3-7-1 Columnar Hexagonal Phase(Colh)之特徵峰鑑定……………………107
3-7-2 Columnar Rectangular Phase(Colr)之特徵峰鑑定…………………108
3-7-3 XRD繞射數據整理…………………………………………………………108
3-8 盤狀液晶體積量測法………………………………………………………114
3-8-1 體積量測公式之推導……………………………………………………114
3-8-2盤狀分子堆疊比較…………………………………………………………117
3-8-3 分子傾斜角度計算………………………………………………………117
3-9 結論…………………………………………………………………………122
參考文獻…………………………………………………………………………123
附圖………………………………………………………………………………127

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