室溫離子熔液應用於無機合成金屬草酸磷酸-甲基磷酸之研究與探討

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曹淳博(Chun-Po Tsao) 查詢紙本館藏

畢業系所

化學學系

論文名稱

室溫離子熔液應用於無機合成金屬草酸磷酸-甲基磷酸之研究與探討
(Ionic liquids as Solvents for Synthesis and Crystallization of Metal Oxalatophosphates and Phosphonates)

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摘要(中)

本論文利用離子熱法順利合成出四個新穎的金屬草酸磷酸鹽及甲基磷酸鹽化合物，化合物 Na2Fe3(C2O4)3(CH3PO3H)2 (I) 為金屬鐵草酸甲基磷酸鹽及等結構的錳化合物Na2Mn3(C2O4)3(CH3PO3H)2 (II)，化合物Cs4Mn6(C2O4)4(HPO4)4.0.5H2O (III) 為一結構複雜性高的錳金屬草酸磷酸鹽三維結構化合物，化合物CsMnAl(PO4)2[(C2O4)0.5]·H2O (IV) 為一錳、鋁混金屬草酸磷酸鹽化合物。在此，將所有化合物以單晶 X-光繞射分析去鑑定化合物的結構以及利用粉末X-光繞射分析、X-光能量分析、熱重分析、梅司堡光譜儀以及傅立葉紅外光譜分析法去鑑定化合物的結構的物性與化性。
化合物(I)(II) 中，金屬八面體互相以共角連結的方式先形成一個三聚體(trimer)的形式，再以草酸及甲基磷酸連接形成一個三維的孔洞骨架，它們兩者為第一個在文獻上被報導利用離子熱法合成的Metal oxalatophosphonates 化合物。化合物(III)為一個草酸同時具有多種配位環境的化合物，金屬多面體先互相以共角連結的方式形成一無限鏈的形式，再與四種環境的草酸根配位基鍵結形成二維的層狀結構，層與層之間靠著磷酸鹽的鍵結形成三維的孔洞骨架。化合物(IV)中，鏈與鏈之間以草酸根以bisbidentate形成互相連結形成二維層狀，最後靠鋁金屬多面體鍵結在層與層之間形成一個三維的孔洞骨架。

摘要(英)

This thesis describes the ionothermal synthesis and structural characterization by single-crystal X-ray diffraction of four new compounds, which include Na2Fe3(C2O4)3(CH3PO3H)2 (I), the Mn analogue, Na2Mn3(C2O4)3(CH3PO3H)2 (II), Cs4Mn6(C2O4)4(HPO4)4.- 0.5H2O (III), and CsMnAl(C2O4)0.5(PO4)2·H2O (IV). The use of ionic liquids as solvents in the reaction are termed ionothermal synthesis to distinguish it from hydrothermal synthesis. All of these four compounds have 3D framework structures which contain alkali metal ions as counter cations.
The 3D framework structure of I comprises a corner-sharing octahedral trimer that is linked with other trimers through two distinct oxalate ligands with unusual linkage types, phosphonate tetrahedra, and H bond to form 10-membered-ring channels where the sodium cations are located. The structure of II has the same structure with structure I. The structure of III connet six distinct MnO6 which are chelate by four units oxalate ligands form 2D layers. Such layers are interconnect by phosphate tetrahedra to form a 3D framework structures. It delimit eight-membered-ring channels in which the cesium cations are located. Compound IV is a oxalato-manganesephosphate structure containing aluminum metal. It has unusual trivalence manganese (Mn3+)metal in this structure. The 3D structure froming two intersected infinite chains, and oxalate ligand linked two manganese octahedra. The cesium cation played role of charge balancing in this structure.

關鍵字(中)

★ 金屬草酸磷酸
★ 離子熔液
★ 離子熱法
★ 甲基磷酸
★ 晶體
★ 離子液體

關鍵字(英)

★ metal oxalatophosphate
★ metal oxalatophosphonate
★ ionothermal
★ crystal
★ ionic liquid

論文目次

第一章緒論…………………………………………………………….1
1-1 簡介…………………………………………………………………1
1-2 離子熔液介紹…………………………………………………1
1-3 離子熔液的發展………………………………………………7
1-4 離子熔液的物理性質…………………………………………9
1-4.1 離子熔液的熱穩定性……………………………….10
1-4.2 離子熔液的密度…………………………………….10
1-4.3 離子熔液的黏度…………………………………….11
1-4.4 離子熔液的溶解力………………………………….12
1-5 實驗儀器設備與單晶X-光繞射晶體結構鑑定……….....12
1-6 磁性物質…………………………………………………….22
第二章金屬草酸-磷酸與甲基磷酸鹽類合成與分析……………….25
2-1 前言……………………………………………………………………….25
2-2 化合物研究與合成………………………………………….30
2-2.1 研究成果…………………………………………….30
2-2.2 離子熔液的合成方法……………………………….33
2-3 實驗流程與化合物合成方法……………………………….38
2-3.1 實驗流程圖………………………………………….38
2-3.2 合成………………………………………………….39
2-4 化合物晶體結構解析……………………………………….42
2-4.1 Na2Fe3(C2O4)3(CH3PO3H)2 (I) 結構解析………44
2-4.2 Na2Mn3(C2O4)3(CH3PO3H)2 (II) 結構解析………45
2-4.3 Cs4Mn6(C2O4)4(HPO4)4.0.5H2O (III) 結構解析.46
2-4.4 CsMnAl(C2O4)0.5(PO4)2·H2O (IV) 結構解析....48
第三章金屬草酸-磷酸與甲基磷酸化合物性質探討……………….50
3-1 前言………………………………………………………….50
3-2化合物 Na2Fe3(C2O4)3(CH3PO3H)2 (I) 性質探討.......50
3-3 化合物Na2Mn3(C2O4)3(CH3PO3H)2 (II) 性質探討......63
3-4 化合物Cs4Mn6(C2O4)4(HPO4)4.0.5H2O (III) 性質探討.65
3-5 化合物CsMnAl(C2O4)0.5(PO4)2·H2O 性質探討.........74
第四章結果與討論........................................80
4-1 前言.............................................80
4-2 化合物Na2Fe3(C2O4)3(CH3PO3H)2 結構描述與討論…….80
4-3 化合物Na2Mn3(C2O4)3(CH3PO3H)2 結構描述與討論…...82
4-4 化合物Cs4Mn6(C2O4)4(HPO4)4.0.5H2O 結構描述與討論.83
4-5 化合物CsMnAl(PO4)2[(C2O4)0.5]·H2O結構描述與討論…86
第五章結論………………………………………...............103
參考文獻………………………………………………………………108
附錄(一) 矽油合成法 ...……………….………………………..112
附錄(二) 化合物(I) - (IV)結構數據、熱擾動參數、原子位置、鍵長相關資料..............................................120
附錄(三) 發表文獻……………………………………...........135

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指導教授

李光華(Kwang-Hwa Lii)

審核日期

2007-7-6

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