臺灣博碩士論文加值系統

(a)本實驗室致力於氟化物之相關的研究，合成短氟鏈聯?啶螯合劑，接上 鈀、鉑金屬，形成含氟鏈之金屬錯合物。而我的研究主要是將氟鏈末端改為 鹵化物(Cl、Br、I)，合成螯合劑，接上鈀、鉑金屬，形成末端含鹵素之短氟 鏈聯?啶金屬錯合物。接著，使用雙溶劑法，控制其析出速度，養出單晶。 再利用不同的儀器(NMR、FT-IR、XRD、熔點測定儀)來鑑定，並搭配理論計 算，比較實驗值和理論值，探討晶體的結構，會發現到同一個金屬錯合物，因為其養晶的條件不同，造成晶體分子間的堆疊方式不同，呈現的顏色也不全然相同，也發現到與氟鏈末端為氫原子不同之處是末端含鹵素之金屬錯合物會形成分子間及分子內鹵素鍵與碳－鹵鍵鍵長的改變。 (b)含氟化合物不僅可以作為鹵素鍵的電子的提供者，也可以做為電子的接受者。本實驗室合成一系列短氟鏈?啶螯合劑以及末端含鹵素短氟鏈?啶螯合劑， 因螯合劑為液體，故我們將螯合劑與鹵化氫(HX, X=Cl、Br、I)、糖精反應形成固體鹽類，利用再結晶，養出單晶。因結構中含有許多弱作用力，故本部分著重在探討其中之非共價鍵結，而含氟鏈?啶鹽類是作為鹵素鍵的接受者。再者，我們也發現， IPFB及1,4-DITFB可作為鹵素鍵的提供者，並且利用拉曼光譜及理論計算分析這些弱作用力的振動光譜，進行一系列的非共價鍵結作用力探討。

(a) Our Lab has been started to synthesize polyfluorinated compounds and promoted their recognition considerably. On continuation of our prior studies, I synthesized Bipyridine ligands having terminal Halogen and its palladium / platinum metal complexes in the research to study their structural properties. The reaction of bipyridine ligands with Palladium and Platinum Metals to generate their corresponding Metal complexes. The synthesized ligands and their metal complexes have been characterized using IR, NMR, Single Crystal X-ray diffraction, and Melting point techniques. We have attempted to prepare crystals with various structures, using dual solvent and change of temperature during recrystallization. With calculation, compared experimental value and theoretical value, to study their structural properties and non-colvalent bond (Halogen Bond). (b) Flourous compounds can be electron donor or electron acceptor. Our Lab has been successfully synthesized a series of fluorine-containing pyridine. Because pyridine ligands are liquid, we used ligands to react with hydrogen halide or saccharin to generate the pyridium salts and pyridium saccharinate salts. We have attempted to prepare crystals with various structures. Because the structure contains many weak interactions, so we focus on the discussion of non-covalent bonding, and fluorine-containing pyridium salts as an acceptor of the halogen bonding. Furthermore, we also found that IPFB and 1,4-DITFB could be used as the donor of the halogen bonding. The Raman spectra and theoretical calculations were used to analyze the vibrational spectra of these weak interactions, and a series of non-covalent bonds to explore.

摘要 i ABSTRACT ii 誌謝 iv 目錄 v 表目錄 viii 圖目錄 x 縮寫對照表 xv (a)含鹵素之短氟鏈聯?啶及其金屬錯合物之合成、結構之相關研究(鹵素鍵) 1 第一章、緒論 2 1-1.前言 2 1-2 相關理論與文獻回顧 3 1-2-1 聯?啶 3 1-2-2 鹵素鍵 4 第二章、實驗方法 6 2-1 藥品材料 6 2-2 儀器 7 2-3 實驗 8 2-3-1 合成螯合劑 8 2-3-2 合成金屬錯合物 10 2-3-3 再結晶 11 2-3-4 螯合劑和鈀、鉑金屬錯合物之鑑定數據 12 第三章、結果與討論 26 3-1 儀器鑑定 26 3-1-1 含氟鏈聯?啶及其金屬錯合物 26 3-2 理論計算 28 第四章、結論 31 圖譜 32 參考文獻 50 (b)含氟化合物作為提供者或接受者之非共價鍵結之探討 53 第一章、緒論 54 1-1.前言 54 1-2 相關理論與文獻回顧 55 1-2-1?啶 55 1-2-2糖精 55 1-2-3?啶與糖精及鹵化氫之鹽類 56 1-2-4 IPFB and 1,4-DITFB 57 第二章、實驗方法 58 2-1 藥品材料 58 2-2 儀器 59 2-3 實驗 60 2-3-1 合成CH2Br-py 60 2-3-2 合成?啶螯合劑 60 2-3-3 合成?啶鹵化鹽類 61 2-3-4 合成?啶糖精鹽類 63 2-3-5 合成IPFB及1,4-DITFB之加成物 67 第三章、結果與討論 75 3-1 非共價鍵結之討論 75 3-1-1 含氟鏈?啶及其鹽類化合物 75 3-1-2 IPFB及1,4-DITFB之加成物 81 第四章、結論 86 圖譜 87 參考文獻 99 附錄A 102 4-2FCl-py-HCl （ i16666） 103 4-8FCl-py-HCl （ i16643） 106 2{5,5-(CH3)2-2,2-bpy}+C6F5I（ i16553） 110 5,5-(CH3)2-2,2-bpy+ C6F4I2（i16729） 115 附錄B 117 C6F4Br2之加成物 118

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