含氮氧原子之硼錯合物液晶性質探討

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雷子暘(Zih-Yang Lei) 查詢紙本館藏

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化學學系

論文名稱

含氮氧原子之硼錯合物液晶性質探討

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摘要(中)

在系列一中成功合成出以salicylideneamines或B-enaminoketonates為配位基1a-c，並與boron difluoride (BF2)形成錯合物1a-c-BF2其中1a-c-BF2皆有液晶相的生成，藉由改變中心結構的共振長度以及增加推電子基，來觀察對液晶行為表現及光學性質的影響。並且由化合物1c-BF2 (n = 10)單晶結構可得知，中心的硼原子為四面體，並且兩苯環之間的兩面角為81.3˚，這也導致了化合物1c-BF2大多缺乏液晶相。化合物1b-BF2擁有SmC的桿狀型液晶相而化合物1a-BF2和1c-BF2則為SmA相。三化合物的放光波長在溶液態λmax = 476-541 nm而在固態時其放光則在λmax = 488-550 nm，而化合物1c-BF2在固態時則具有AIEE (Aggregation induced enhanced emission)，可做為一良好的發光材料。
第二系列成功以B-enaminoketonates作為主體，以不同的連接基做置換並與boron difluoride (BF2)形成錯合物2-3-BF2，其中化合物2b-BF2 (n = 12, m = 2, 3)和2c-BF2並無液晶相產生，而以萘環取代苯環的化合物3b-BF2 (m = 2, 3)和3c-BF2因為擁有較平整的分子平面，分子間的堆疊較好因此可誘導出液晶相。經由偏光紋理圖與powder X-ray diffraction實驗結果判定2a-BF2、2b-BF2 (n = 12, m = 0)、3a-BF2、3b-BF2 (m =2)為SmC桿狀液晶，而3b-BF2 (m =3)和3c-BF2為SmA桿狀液晶。另外從培養出的化合物2a-BF2 (n = 12)單晶探討分子之排列情形與作用力多寡。化合物23-BF2以UV可見光光譜、螢光光譜探討該分子的光學性質，從結果可得知中心結構以苯環或者直接相連接時，因延伸其共振使得最大的放光波長紅移，即 max = 523 (2a-BF2), 518 (2b-BF2 (m = 0)), 538 (3a-BF2)。放光為黃綠色光。

摘要(英)

In the first part, Three new families of borondifluoride complexes 1a-c-BF2 derived from salicylideneamines 1a and B-enaminoketonates 1b-c were reported, and their mesomorphic and optical properties were also investigated. One single crystal and molecular structure of nonmesogenic BF2 complex 1c-BF2 (n = 10) was resolved and the geometry of the central boron atom was tetrahedron. A larger dihedral angle of 81.3˚ between the two phenyl rings observed in crystal lattice was contributed to the lack of liquid crystallinity. Boron complexes 1a-BF2 formed monotropic SmA phases, while boron complexes 1b-BF2 exhibited enantiotropic SmC mesophases. The optical property of the boron complexes was dependent on their molecular structures, and they emitted a blue-to-green emission at max = 476-541 nm in the solution and 488-550 nm in the solid state. The
1c-BF2 have the property of AIEE (Aggregation-induced enhanced emission), and it can be a protential material of luminescence. In the second part, two new series of bis-(boron difluoride) complexes 2-3-BF2 derived from substituted B-enaminoketonates 2-3 were reported, and their mesomorphic and optical properties were also investigated. 2b-BF2 (n = 12, m = 2, 3) and 2c-BF2 were not mesogens. The single crystal of mesogenic boron complex 2a-BF2 (n = 12) was obtained, and its single crystal and molecular structures were resolved. Results appeared that bis-(BF2) complexes 2a-BF2, 2b-BF2 (n = 12, m = 0), 3a-BF2 and 3b-BF2 (m =2) exhibited smectic C phases. However, 3b-BF2 (m =3) and 3c-BF2 exhibited smectic A phases. In the result, the emission of 2a-BF2, 2b-BF2 and 3a-BF2 red shift to 523, 518 and 538 nm respectively because of their resonance structure. Also, their colors of emission are yellow-green.

關鍵字(中)

★ 液晶

關鍵字(英)

★ liquid crystal

論文目次

中文摘要 i
Abstract ii
謝誌 iii
第一章緒論 1
1-1 液晶簡介 2
1-2 液晶相形成條件 3
1-3 液晶相分類 5
1-3-1 向列型液晶 6
1-3-2 層列型液晶 6
1-3-3 盤狀液晶 7
1-4 Boron difluoride complex簡介 8
1-5 研究動機 10
1-5-1 系列一研究動機 10
1-5-2 系列二研究動機 11
第二章實驗部分 13
2-1 實驗藥品 14
2-2 儀器設備 16
2-3 實驗流程 19
2-3-1系列一之實驗流程 19
2-3-2系列二之實驗流程 20
2-4實驗步驟 22
2-4-1系列一之合成 22
2-4-2系列二之合成 37
第三章結果與討論 54
3-1 系列一化合物之探討 55
3-1-1系列一之結構與代號 55
3-1-2系列一化合物1H NMR探討 56
3-1-3系列一化合物之偏光紋理圖(POM) 57
3-1-4系列一化合物之熱微差掃描分析儀(DSC) 60
3-1-5系列一化合物1-BF2之單晶結構探討 63
3-1-6系列一化合物1-BF2之熱重量分析結果 69
3-1-7 化合物 1-BF2之Powder X-ray分析與分子模擬排列 70
3-1-8系列一化合物之紅外線光譜分析 73
3-1-9系列一化合物1-BF2光學性質探討 74
3-2 系列二化合物性質探討 78
3-2-1系列二之結構與代號 78
3-2-2系列二化合物之偏光紋理圖(POM) 79
3-2-3系列二化合物之熱微差掃描分析儀(DSC) 82
3-2-4系列二化合物之熱重分析(TGA) 85
3-2-5系列二化合物之 Powder X-ray 分析 86
3-2-6系列二化合物2a-BF2之單晶探討 88
3-2-7系列二化合物光學性質探討 95
第四章結論 98
4-1 系列一結論 99
4-2 系列二結論 100
參考文獻 101
附圖 106
附表 159

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指導教授

賴重光(Chung-Kuang Lai)

審核日期

2018-7-10

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