呋喃衍生物及其硼錯合物之液晶性質探討

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姓名

李庭安(Ting-An Lee) 查詢紙本館藏

畢業系所

化學學系

論文名稱

呋喃衍生物及其硼錯合物之液晶性質探討

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摘要(中)

本研究以五員雜環呋喃 (furan) 作為核心，以 α, β-二酮(α,β-diketonate) 連接外圍苯環結構之烷氧長碳鏈合成配位基 1a-d，並進而與 BF2 配位形成錯合物 1a-BF2-1d-BF2，以及合成吡唑 (pyrazole) 衍生物 2a-d。由化合物 1d (n = 0) 單晶結構得知晶系為單斜晶系(monoclinic)，空間群為 P21/n，分子形狀為馬蹄型，且兩側苯環與雜環呋喃之二面角分別為 16.582o 與 25.292o。所有的配位基1a-d 均為結晶相，而化合物 1d-BF2、 2a 與 2d 具有 SmA 及 SmC 的液晶相性質。從螢光放光光譜中，可得知硼錯合物 1a-BF2-1d-BF2 (n = 12) 的螢光放光範圍為 max = 520-624 nm，放光為綠光至紅光範圍;而吡唑衍生物 2a-d (n = 12) 的螢光放光範圍為 max = 355-360 nm，放光為紫外光範圍。此外，可發現硼錯合物之最大放光波長皆比配位基紅移，而在固態螢光光譜中，化合物 1d-BF2 (n = 12) 所測得之放光波長為 max = 618 nm，在溶液態所測得之放光波長為 max = 549 nm，可得知化合物 1d-BF2 (n = 12) 在固態所測得之放光波長較溶液態紅位移，此為 J-aggregate 堆疊所導致。

摘要(英)

In this work, four new families of borondifluoride complexes 1a-BF2-1d-BF2 and four new families of pyrazole derivatives 2a-d derived from , -ketonate furans 1a-d were reported and their mesomorphic properties investigated. One single crystallographic structure of mesogenic complex 1d (n = 0) was determined X-ray analysis; it crystallizes in a monoclinic space group P21/n. The crystal was shaped as a horsesho. The dihedral angles of the furan ring and the benzene ring on both side are 16.582o and 25.292o respectively. All ligands 1a-b were crystals, however, all bis(BF2) complexes 1d-BF2, 2a and 2d formed SmA or/and SmC phases. The optical property of the bis(BF2)2 complexes 1a-BF2-1d-BF2 (n = 12) was related with their molecular structures, and they emitted green-to-red emissions at max = 520-624 nm in CH2Cl2. Pyrazole derivatives 2a-d (n = 12) emitted ultraviolet emissions at max = 355-360 nm in CH2Cl2. The maximum luminescent emission of the compounds 1a-BF2-1d-BF2 (n = 12) were red-shifted compared to the compounds 1a-d. Furthermore, the maximum luminescent emission of bis(BF2) complex 1d-BF2 (n = 12) in the solid state (max = 618 nm) was red-shifted compared to in the solution (max = 549 nm) because of the J-aggregate.

關鍵字(中)

★ 呋喃
★ 液晶
★ 二氟化硼

關鍵字(英)

★ furan
★ Liquid crystal
★ boron difluoride

論文目次

目錄
中文摘要 I
Abstract II
謝誌 III
目錄 V
圖目錄 VIII
表目錄 XI
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 液晶作用力 5
1-4 液晶形成方式分類 7
1-4-1 向列型液晶 (Nematic liquid crystal) 9
1-4-2 層列型液晶 (Smectic liquid crystal) 9
1-4-3 盤狀液晶 (Columnar liquid crystal) 10
1-5 Boron difluoride complexes 簡介 11
1-6 五員雜環簡介 13
1-7 研究動機 15
第二章實驗部分 17
2-1 實驗藥品 18
2-2 儀器設備 20
2-3 實驗流程 24
2-4 實驗步驟 25
2-4-1 系列之合成 25
第三章結果與討論 50
3-1 化合物性質探討 51
3-1-1 結構與代號 51
3-1-2 化合物 1H NMR與 19F NMR 探討 52
3-1-3 化合物 1d (n = 0) 之單晶結構探討 56
3-1-4 化合物之偏光紋理圖 (POM) 63
3-1-5 化合物之熱微差掃描分析儀 (DSC) 68
3-1-6 化合物之熱重分析 (TGA) 75
3-1-7 化合物子模擬排列 78
3-1-8 化合物之光學性質探討 85
第四章結論 90
4-1 結論 91
第五章曾製備過之無液晶相結構 93
5-1 曾製備之結構一 94
5-1-1 曾製備之結構一之偏光紋理圖 97
5-2 曾製備之結構二 98
5-2-1 曾製備之結構二之偏光紋理圖 100
5-3 曾製備之結構三 101
5-3-1 曾製備之結構三之偏光紋理圖 103
5-4 曾製備之結構四 104
5-4-1 曾製備之結構四之偏光紋理圖 108
參考文獻 109
附圖 115
附表 150

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指導教授

賴重光(Chung-Kuang Lai)

審核日期

2021-7-21

推文