本論文主要在研究新型聯吡啶鹽類(2,2’-bipyridnium)的離子液體及奈米材料上的應用。聯吡啶的製備參考相關文獻修正後，合成出帶有烷基長碳鏈的醯胺、酯官能基化合物，在將這些化合物合成的三系列離子化合物。聯吡啶基鹽離子化合物共有Cl-、Br-、I-、PF6-、ClO4-、BF4-、TFA及Triflate八種陰離子。由實驗結果發現化合物10c dibutyl-1-methyl-2,2’-bipyridnium-3,3’-dicarboxylate tetrafluoroborate有最低的熔點；陽離子烷基長度與熔點的關係，以理論計算統計出偶極距與熔點表現曲線並探討之間的相對關係，低偶極距會有高熔點、高偶極距有低熔點的行為表現。在奈米金粒子方面的探討，以自行合成的新穎離子液體添加到奈米金溶液，離子化合物修飾在奈米金粒子表面上，使金粒子之間的距離靠近卻不會聚集產生沉澱，並改變奈米金粒子的形狀，成功的修飾奈米金粒子，未來探討其應用的價值。

Ionic liquids, ionic salts with melting point lower than 100 degree, can be regarded as the media for chemical reactions. The nonvolatile nature of ionic liquid gives us significant advantage in minimizing solvent consumption. Not only providing eco-friendly reaction media but ionic liquids share the important physical property of highly thermal stable ability and exhibiting quite distinct chemical properties in terms of polarity, nucleophilicity and hydrogen bonding properties. These ionic liquids have attracted much attention as promising green solvents in recent years.
    The reactions of 2,2’-bipyridine-3,3’ –dicarboxylic acid , N,N’ -dialkyl-2,2’-bipyridine-3,3’-dicarbamide and dialkyl-2,2’-bipyridine -3,3’-dicarboxylate and with alkyl iodide obtain three series of salts. Then the anion exchange reaction was carried out to transform these iodide salts into other anions form, for example, chloride, bromide, perchlorate, hexafluorophosphate, trifluoroacetate, trifluoromethanesulfonate, etc. These ionic compounds have lower melting points. Some of them are lower than 100 degree. We added ionic liquids into sphere gold nanoparticle solution, and we got new nanostructure.

中文摘要

英文摘要

第一章 緒論…………………………….…………….………….…1

第二章 實驗部份
2-1藥品…………………………….……….………….…………..10
2-2代號及簡稱…………………………….……….………….…..10
2-3合成…………………………….………….………….………..17
2-4物理鑑定儀器…………………………….……………………32

第三章 結果與討論
3-1 羧基聯吡啶化合物…………………………….…………...…34
3-1-1  晶體結構…………………………….…………………..34
3-1-2  氫核磁共振光譜…………………………….…………..39
3-1-3  電子吸收光譜…………………………….……………..40
3-2醯胺基聯吡啶化合物…………………………….……………41
3-2-1  氫核磁共振光譜…………………………….…………..41
3-2-2  電子吸收光譜…………………………….……………..42
3-2-3  紅外光譜…………………………….…………………..43
3-2-4  離子液晶…………………………….…………………..44
3-3酯基聯吡啶化合物…………………………….…………...….46
3-3-1  氫核磁共振光譜…………………………….…………..46
3-3-2  電子吸收光譜…………………………….……………..47
3-3-3  紅外光譜…………………………….…………………..49
3-4 離子液體……………………………………….…………...…50
3-4-1  理論計算…………………………….…………...……..50
3-4-2  熱穩定度………………………………..….…………...54
3-4-3  奈米金粒子應用…………………………….…..……...57

第四章 結論…………………………….………………………….72

參考文獻…………………………….………………………………73

附錄…………………………….…………………………………….76

圖目錄
圖1 6a ORTEP 圖…………………………….…………........35
圖2 6a bc 平面單晶堆疊圖…………………………..…….36
圖3 6a ab 平面單晶堆疊圖…………………………..…….36
圖4 6a 單晶堆疊圖……………………….………..…….....37
圖5 6b 幾何最佳化結構圖…………………………..…….....39
圖6 1, 6a, 6b 電子吸收光譜……………………….….…...…40
圖7 2a~2d 電子吸收光譜…………………………...….…….42
圖8 7a~7d 電子吸收光譜……………………….….………...42
圖9 8a~8f 電子吸收光譜………………………….………...43
圖10 鹵化鈀離子液晶結構…………………………….……...44
圖11 7c, (C16AM)2PdI4電子吸收光譜…………….………….45
圖12 8a, (C16AM)2PdCl4 電子吸收光譜……………………...45
圖13 8b, (C16AM)2PdBr4電子吸收光譜……………………...45
圖14 3a~3h電子吸收光譜……………………….……………47
圖15 9a~9h 電子吸收光譜……………………….………...…48
圖16 10a~10h 電子吸收光譜……………………….…………48
圖17 Biox salt1 ORTEP 圖……………………….……………51
圖18 Biox salt1 幾何最佳化結構圖……………………….….51
圖19 9a~9f 偶極距圖……………………….……………..….53
圖20 9a~9f 熔點圖……………………….…………………...53
圖21 10a~10e 液態溫度範圍圖……………………….………54
圖22 10a 熱重分析微分圖……………………….……………55
圖23 10a 熱重分析圖……………………….…………………55
圖24 10b 熱重分析微分圖……………………….……………56
圖25 10b 熱重分析圖……………………………………….…56
圖26 奈米金 電子吸收光譜……………………………….…..57
圖27 奈米金50,000 倍放大SEM圖…………………………..58
圖28 奈米金90,000 倍放大SEM 圖…………………..……..58
圖29 10c 50,000 倍放大SEM 圖……………………………..59
圖30 10c 200,000 倍放大SEM 圖……………………………59
圖31 奈米金添加10b 電子吸收光譜…………………………61
圖32 奈米金添加10e 電子吸收光譜………………………....61
圖33 GNPs+10b 5 萬倍放大………………………………...62
圖34 GNPs+10b 20 萬倍放大……………………………....…62
圖35 GNPs+10e 10 萬倍放大………………………………....62
圖36 GNPs+10e 20 萬倍放大…………………………………62
圖37 奈米金添加低濃度10c 電子吸收光譜…………………64
圖38 奈米金添加高濃度10c 電子吸收光譜…………………64
圖38 奈米金添加5 電子吸收光譜……………………………64
圖39 GNPs+10c 1.5 萬倍放大………………………..……..65
圖40 GNPs+10c 5 萬倍放大………………………...………65
圖41 GNPs+10c 5 萬倍放大…………………...……………65
圖42 GNPs+10c 10 萬倍放大……………………………….65
圖43 GNPs+10c 20 萬倍放大……………...………………..66
圖44 奈米金添加低濃度5 電子吸收光譜……………………68
圖45 奈米金添加高濃度5 電子吸收光譜……………………68
圖46 GNPs+5 1 萬倍放大…………………..……………….69
圖47 GNPs+5 10 萬倍放大………………………………….69
圖48 GNPs+5 1.5 萬倍放大…………………………………70
圖49 GNPs+5 6 萬倍放大…………………………………...70
圖50 GNPs+5 20 萬倍放大………………………………….71
圖51 GNPs+5 20 萬倍放大………………………………….71
附圖目錄
附圖1 6a 氫核磁共振光譜………………………………….…..76
附圖2 6b 氫核磁共振光譜 in CDCl3…………………………..77
附圖3 6b 氫核磁共振光譜 in d6-DMSO……………………....78
附圖4 2c 氫核磁共振光譜 in CDCl3………………………......79
附圖5 2c 氫核磁共振光譜 in CDCl3+1 drop D2O………….….80
附圖6 7c 紅外光譜……………………………………………...81
附圖7 8c 紅外光譜……………………………………………...82
附圖8 8d 紅外光譜……………………………………………...83
附圖9 8e 紅外光譜……………………………………………...84
附圖10 8f 紅外光譜………………………………………………85
附圖11 9b 氫核磁共振光譜 in CDCl3…………………………..86
附圖12 10a 氫核磁共振光譜 in CDCl3…………………………87
附圖13 10b 氫核磁共振光譜 in CDCl3…………………………88
附圖14 10c 氫核磁共振光譜 in CDCl3…………………………89
附圖15 10d 氫核磁共振光譜 in CDCl3…………………………90
附圖16 10e 氫核磁共振光譜 in CDCl3…………………………91
附圖17 9b 紅外光譜………………………………………….…..92
附圖18 10a 紅外光譜……………………………………….……93
附圖19 10b 紅外光譜……………………………………….……94
附圖20 10c 紅外光譜……………………………………….……95
附圖21 10d 紅外光譜……………………………………….……96
附圖22 10e 紅外光譜……………………………………….……97
附圖23 9b 熱重分析圖…………………………………….……..98
附圖24 10c 熱重分析圖………………………………….………99
附圖25 10d 熱重分析圖………………………………….……..100
附圖26 10e 熱重分析圖………………………………………...101
表目錄
表1 6a 晶格參數……………………………………………….38
表2 9a,10a~10e 氫核磁共振位移數據………………………..46
表3 6a 晶體數據與理論計算數據…………………………….52
表4 9a~9f 理論計算偶極距數據………………………………53
表5 9a~9f 熔點數據……………………………………………53

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