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研究生:彭偉承
研究生(外文):Peng, Wei-Cheng
論文名稱:以POSS為核心單元之單分子四重夾設計及其主客體端點修飾
論文名稱(外文):Design of POSS-Based Molecular Quaternary Clips and End-functionalization of Host-Guest Complexes
指導教授:王建隆
指導教授(外文):Wang, Chien-Lung
口試委員:許千樹鍾文聖吳彥谷王建隆
口試委員(外文):Hsu, Chain-ShuChung, Wen-ShengWu, Yen-KuWang, Chien-Lung
口試日期:2019-03-25
學位類別:碩士
校院名稱:國立交通大學
系所名稱:應用化學系碩博士班
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2019
畢業學年度:107
語文別:中文
論文頁數:84
中文關鍵詞:主客化學分子夾單分子四重夾多面體聚矽氧烷衍生物萘二醯亞胺衍生物
外文關鍵詞:Host-Guest ChemistryMolecular ClipsQuaternary Molecular ClipsPOSS derivativesNDI derivatives
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分子夾在主客化學領域中因溶解度佳,容易修飾官能基以及相對於傳統環形主體有更彈性的空間去夾取客體,使其逐漸發展起來;但是目前的分子夾以單夾或單分子雙夾為主,超過雙夾以上的分子夾尚未被報導過,使得分子夾的多樣性及功能性受到了限制。在本篇論文中,成功以POSS為核心單元合成了Q clip單分子四重夾。POSS被認為是最小的氧化矽奈米粒子,其粒徑約0.5-0.8奈米。在POSS核心的八個頂點上修飾上不同的共軛取代基,可形成三維共軛巨分子。我們利用POSS核心所建立起的空間以及其設計頂點修飾多電子的芘 (pyrene)為官能基,藉由電荷轉移作用力可以夾取4當量的萘二醯亞胺衍生物(Naphthalene diimide, NDI)Hex-NDI;且Q clip在夾取Hex-NDI形成主客體複合物的過程中,能夠收斂芘(pyrene)的官能基手臂,使原本為不定形態(amorphous)的Q clip能形成柱狀相,並形成層列型液晶相。另外,Q clip對於官能化修飾的萘二醯亞胺衍生物Py-NDI, Amine-NDI, OH-NDI同樣具有選擇性,能夠夾取4當量的客體分子並形成柱狀相;最後,我們可以利用官能化的NDI,並經由添加劑的加入,對主客體奈米柱的端點進行官能化修飾,修飾上不同的分子間作用力,為分子夾添增了功能性以及多樣性。
Molecular clips are developing in host-guest chemistry because of good solubility, easier to functionalized and more flexible space to clamp guest than traditional macrocycles. The number of clips in molecular clips which is bigger than 2 has never been reported, and the versatility and functionality of molecular clips has been restricted. In this thesis, we use POSS nanoparticle as unit core to synthesize Q clip, which is molecular quaternary clip. POSS is considered to be the smallest silicon nanoparticle, and size is 0.5-0.8 nm. Functionalize different conjugate groups onto the eight vertices of POSS and three dimension giant molecule would be formed. We use the space built up by POSS and functionalize electron-rich pyrene onto POSS. Q clip can clamp 4 equivalent of Hex-NDI by charge transfer interaction. In the formation of host-guest complex, Q clip would be conformation change from amorphous to rod-like by the elongation of functional groups in Q clip. However, Q clip can clamp 4 equivalent of functionalized NDI derivatives such as Py-NDI, Amine-NDI and OH-NDI. Last, we can functionalize the end-side of host-guest nanorod by noncovalent interactions between functionalized NDI and additive. We have successfully pioneer the functionality and versatility of molecular clips.
摘要 i
Abstract ii
致謝 iii
目錄 iv
圖目錄 viii
Scheme目錄 xii
第一章 緒論 1
1.1 前言 1
1.2 分子間作用力 1
1.2.1 電荷-電荷作用力5 2
1.2.2 電荷-偶極作用力5 3
1.2.3 偶極-偶極作用力5 4
1.2.4 偶極-誘導偶極作用力5 5
1.2.5 誘導偶極-誘導偶極作用力5 5
1.2.6 氫鍵作用力 6
1.2.7 π-π作用力 6
1.2.8 金屬配位 7
1.3 環狀主體分子 8
1.3.1 冠醚 (Crown ether) 8
1.3.2 穴醚 (Cryptands) 9
1.3.3 葫蘆脲6 (Cucurbiturils, CB) 9
1.3.4 芳杯7 (Calixarenes) 10
1.3.5 環糊精8 (Cyclodextrin, CD) 11
1.4 非環狀主體分子 – 分子夾子與鑷子(Molecular clips and tweezers) 11
1.4.1 單夾 12
1.4.2 單分子雙夾 13
第二章 緒論與動機 15
2.1 多面體低聚矽氧烷( Polyhedral oligomeric silsesquio-xanes, POSS) 15
2.1.1 POSS衍生物結構分析 17
2.1.2 由Pyrene-NDI組成之電荷轉移作用力 18
2.2 研究動機 19
第三章 實驗結果與討論 21
3.1 分子合成 21
3.1.1 主體分子Q-clip之合成 21
3.1.2 客體分子Hex-NDI之合成 21
3.2 分子鑑定 22
3.2.1 主體分子Q clip結構鑑定 22
3.2.2 客體分子Hex-NDI結構鑑定 24
3.3 熱穩定性分析 26
3.4 Q clip/Hex-NDI混摻物樣品製備 27
3.5 Q clip/hex-NDI混摻物之固態及溶液態超分子結構 27
3.5.1 Q clip分子夾形成超分子結構的最佳比例 27
3.5.2 主客體錯合物的WAXD結構分析 29
3.6 官能化客體分子合成 32
3.6.1 官能化NDI之合成 32
3.7 官能化客體分子鑑定 33
3.7.1 客體 – Py-NDI之鑑定 33
3.7.2 客體 – Amine-NDI之鑑定 36
3.7.3 客體 – OH-NDI之鑑定 38
3.8 官能化客體分子熱穩定性分析 40
3.9 Q clip/Py-NDI、Q clip/Amine-NDI、Q clip/OH-NDI主客體奈米柱製備 42
3.10 官能化主客體奈米柱製備 42
3.10.1 以金屬配位修飾端點之超分子主客體 43
3.10.2 以酸鹼作用力修飾端點之超分子主客體 43
3.10.3 以氫鍵作用力修飾端點之超分子主客體 43
3.11 Q clip/Py-NDI主客體結構分析與奈米柱端點修飾 43
3.11.1 Q clip/Py-NDI超分子之相變探討 43
3.11.2 Q clip/Py-NDI超分子之結構分析 44
3.11.3 Q clip/Py-NDI奈米柱作用力探討與端點修飾金屬配位力 46
3.12 Q clip/Amine-NDI主客體結構分析與奈米柱端點修飾 49
3.12.1 Q clip/Amine-NDI超分子之相變探討 49
3.12.2 Q clip/Amine-NDI超分子之結構分析 50
3.12.3 Q clip/Amine-NDI奈米柱作用力探討與端點修飾金屬配位力 51
3.13 Q clip/OH-NDI主客體結構分析與奈米柱端點修飾 54
3.13.1 Q clip/OH-NDI超分子之相變探討 54
3.13.2 Q clip/OH-NDI超分子之結構分析 55
3.13.3 Q clip/OH-NDI超分子奈米柱端點修飾氫鍵作用力 57
第四章 結論 58
第五章 實驗部分 59
5.1 試藥來源 59
5.2 測量儀器 59
5.2.1 核磁共振儀 (Nuclear Magnetic Resonance Spectrometer,NMR) 59
5.2.2 熱重分析儀 (Thermal Gravimetric Analyzer,TGA) 59
5.2.3熱差掃描卡計 (Differential Scanning Calorimeter,DSC) 60
5.2.4 光學顯微鏡 (Optical Microscope,OM) 60
5.2.5 廣角X光繞射儀 (Wide Angle X-ray diffraction,WAXD) 60
5.3 合成部分 61
5.3.1 化合物1之合成 61
5.3.2 Q clip之合成 62
5.3.3 Hex-NDI之合成 63
5.3.1 化合物2之合成 63
5.3.2 Py-NDI之合成 64
5.3.3 Amine-NDI之合成 65
5.3.4 OH-NDI之合成 65
第六章 附圖 67
第七章 參考資料 83
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