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研究生: 吳怡瑩
Yi-Ying Wu
論文名稱: 有機-無機混合配位基化合物之合成、結構鑑定及性質探討
Synthesis, Crystal Structures and Properties of Organic-Inorganic Hybrid Compounds(H4A)[U2F6(C2O4)3]‧4H2O (A = TREN, APPIP)M(H2O)(C2O4)0.5(HPO3)‧H2O (M = Er, Yb)
指導教授: 李光華
Kwang-Hwa Lii
口試委員:
學位類別: 碩士
Master
系所名稱: 理學院 - 化學學系
Department of Chemistry
畢業學年度: 95
語文別: 中文
論文頁數: 103
中文關鍵詞: 水熱法草酸氟氧化鈾鑭系草酸亞磷酸
外文關鍵詞: hydrothermal, uranium fluorooxalate, Lanthanide Oxalatophosphites
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  • 有機-無機混合配位基化合物之合成是近年來的熱門研究領域之一,原因在於混合配位基常會使化合物具有趣的物理性質與結構的新穎性,而本研究以中溫水熱合成法成功合成出四個有機-無機混合配位基化合物,並依照配位基的不同將其分為兩系列。此研究共合成出三個新穎結構之化合物,茲將化合物列於下方:
    A系列:(H4A)[U2F6(C2O4)3]‧4H2O (A = TREN, APPIP)
    B系列:M(H2O)(C2O4)0.5(HPO3)‧H2O (M = Er, Yb)
    以上所列之化合物均能得到單晶,利用單晶X-光繞射儀進行結構解析、定出化學式,之後以粉末X-光繞射分析確定產物的純度及元素分析 (EA) 確定化合物中C、H、N元素比例,並利用熱重分析(TGA) 研究化合物的熱性質,最後利用超導量子干涉磁量儀 (SQUID)來量測化合物的磁性現象。
    A系列化合物是利用不同的結構導引試劑以中溫水熱法反應得到化合物 A1、A2,它們是第一個具有機模板的草酸氟化鈾化合物,其結構是由六個草酸根以雙邊雙螯的方式交替連接六個UF3O6多面體進而形成具有十二員環的二維層狀結構,有機陽離子與水分子填充於層間。
    B系列化合物是具有中性骨架的草酸亞磷酸化合物,其結構是由LnO8多面體共邊連接形成一條Z字形鏈,再經由 HPO3 以共邊、共角的方式連接形成具四員環的二維層狀結構,再以草酸根以雙邊雙螯的方式連接層與層,進而形成具有八員環的三維中性骨架結構。


    Four organic-inorganic hybrid compounds, (H4A)[U2F6(C2O4)3]‧4H2O [A = tris(2-aminoethyl)amine (A1) and 1,4-bis-(3-aminopropyl)piperazine (A2)] and M(H2O)(C2O4)0.5(HPO3)‧H2O [M = Er (B1) and Yb (B2)], have been synthesized by hydrothermal methods and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic analysis.
    Both A1 and A2 consist of anionic layers, [U2F6(C2O4)3]4-, separated by organic ammonium cations and lattice water molecules. The UF3O6 polyhedra are connected by oxalate ligands with different types within the layers. A1 and A2 are the first example of organically-templated uranium fluorooxalates.
    Both B1 and B2 comprise LnO8 decahedra and HPO3 tetrahedra forming 2-D layers which connected via bisbidentate oxalate anions to form a 3-D framework, and delimit 8-membered ring channels alone a axis. B1 and B2 are the first example of lanthanide oxalatophosphite.

    第一章 緒論 1 1-1 簡介 1 1-2 合成方法簡介 5 1-2-1 水熱法 5 1-2-2 使用藥品清單 10 1-3 鑑定方法 11 1-3-1 使用的儀器及機型 11 1-3-2 單晶X-光繞射實驗與晶體結構解析 12 1-3-3 粉末X-光繞射分析 19 1-3-4 熱重量分析 19 1-3-5 元素分析 19 1-3-6 傅立葉紅外線吸收光譜分析 20 1-3-7 超導量子干涉磁量儀磁性分析 21 1-4 研究成果 24 第二章 含有機模板之草酸氟化鈾 26 2-1 前言 26 2-2輻射之相關常識 30 2-3 合成 32 2-3-1 化合物的反應方法 32 2-3-2 實驗部分 33 2-3-2-1 (H4TREN)[U2F6(C2O4)3]‧4H2O (A1) 合成條件 33 2-3-2-2 (H4APPIP)[U2F6(C2O4)3]‧4H2O (A2) 合成條件 33 2-4 單晶X-光結構解析 34 2-4-1 (H4TREN)[U2F6(C2O4)3]‧4H2O (A1) 晶體結構解析 34 2-4-2 (H4APPIP)[U2F6(C2O4)3]‧4H2O (A2) 晶體結構解析 35 2-5 化合物鑑定 36 2-5-1 粉末X-光繞射分析 36 2-5-2 元素分析 37 2-5-3 熱重量分析 38 2-5-4 傅立葉紅外線吸收光譜分析 40 2-6 結果與討論 42 2-6-1 化合物A1的結構描述與物性測量 42 2-6-1-1 結構描述 42 2-6-1-2 物性測量-磁性探討 45 2-6-2 化合物A2的結構描述與物性測量 48 2-6-2-1 結構描述 48 2-6-2-2 物性測量-磁性探討 51 第三章 金屬草酸亞磷酸化合物 53 3-1 前言 53 3-2 合成 57 3-2-1 化合物的反應方法 57 3-2-2 實驗部分 58 3-2-2-1 Er(H2O)(C2O4)0.5(HPO3)‧H2O (B1)合成條件 58 3-2-2-2 Yb(H2O)(C2O4)0.5(HPO3)‧H2O (B2)合成條件 58 3-3 單晶X-光結構解析 59 3-3-1 Er(H2O)(C2O4)0.5(HPO3)‧H2O (B1) 59 3-3-2 Yb(H2O)(C2O4)0.5(HPO3)‧H2O (B2) 60 3-4 化合物鑑定 61 3-4-1 粉末X-光繞射分析 61 3-4-2 元素分析 62 3-4-3 熱重量分析 63 3-4-4 熱處理 65 3-4-5 傅立葉紅外線吸收光譜分析 67 3-5 結果與討論 69 3-5-1 結構描述 69 3-5-2 結構比較 70 3-5-3 物性測量-磁性探討 75 第四章 結論 76 參考文獻 79 附錄A A系列晶體數據 85 附錄B B系列晶體數據 96 附錄C 發表文獻 103

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