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    題名: 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
    作者: 曹淳博;Chun-Po Tsao
    貢獻者: 化學研究所
    關鍵詞: 金屬草酸磷酸;離子熔液;離子熱法;甲基磷酸;晶體;離子液體;metal oxalatophosphate;metal oxalatophosphonate;ionothermal;crystal;ionic liquid
    日期: 2007-06-26
    上傳時間: 2009-09-22 10:16:53 (UTC+8)
    出版者: 國立中央大學圖書館
    摘要: 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。 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.
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