臺灣博碩士論文加值系統

本研究內容是以金屬離子與有機配基利用自組裝(self-assembly)的方式來合成一系列的金屬-有機材料(metal-organic materials, MOMs)。這裡選用含四氮的五員雜環分子(tetrazoles)，2,3-di-1H-tetrazol-5-ylpyrazine (H2dtp)，與銅、錳金屬鹽類反應得到(NH2Me2)[CuIdtp] (1)、(NH2Me2)4[Mdtp2Cl2] M = Cu2+ (2)、Mn2+ (3)。之後使用另一含三個羧酸根(carboxylate)的配基，4,4′,4′′-s-triazine-1,3,5-triyltri-p-aminobenzoic acid (H3TATAB)，則合成出(NH2Me2)3[In(TATAB)2]．2DMF (4)、(NH2Me2)3[In3(TATAB)4]．3DMF．20H2O (5)、[Cu3(TATAB)2(H2O)3] (6)。X光單晶繞射(single-crystal X-ray diffraction)顯示1為二維平面，2、3為零維分子，4是一維鏈狀，5、6則是三維網狀結構，其中6存在二次穿插的情形。利用PLATON計算5、6的孔洞率分別得到61.4%、66.2%的數值。熱重分析(thermogravimetric analyses, TGA)與粉末繞射(powder X-ray diffraction)顯示1結構維持熱穩定到340℃，5、6趕除空間中客體分子後，無法維持原結構。放光光譜(emission spectra)推斷所有的化合物都有一放光，來自配位基內的躍遷，而1-3則有另一新的波峰為金屬到配基的電子躍遷(metal-to-ligand charge transfer, MLCT)。

Here we report that the self-assembly of serveral metal ions and ligands leads to the formation of a series of metal-organic materials (MOMs). The choice of tetrazolate-based ligand, 2,3-di-1H-tetrazol-5-ylpyrazine (H2dtp) results in (NH2Me2)[CuIdtp] (1) and (NH2Me2)4[Mdtp2Cl2] ( M = Cu2+ (2), Mn2+ (3) ), while 4′,4′′-s-triazine-1,3,5-triyltri-p-aminobenzoic acid (H3TATAB) affords (Me2NH2)3[In(TATAB)2]．2DMF (4), (NH2Me2)3[In3(TATAB)4]．3DMF．20H2O (5) and [Cu3(TATAB)2(H2O)3] (6). Single-crystal X-ray diffraction studies indicate 1 has a 2D structure, 2 and 3 are discrete molecules, 4 is one-dimensional, 5 and 6 are 3D networks, of which two-fold interpenetration is observed in 6. Porosity calculations for 5 and 6 based on PLATON, suggest 61.4% and 66.2% void space for 5 and 6, respectively. Thermal stability of compounds 1, 5 and 6 were studied by thermal analyses and powder X-ray diffraction. As a result, 1 is thermally stable up to 340℃, whereas the structures of 5 and 6, appear to collapse into amorphous phases upon the removal of solvent molecules. The luminescent emissions for all compounds were also measured. Bands due to intra-ligand transitions were observed. In addition, compounds 1, 2, and 3 also exhibit new bands, which can be attributed to metal-to-ligand charge transfer (MLCT).

目錄 ------------------------------------------I
圖目錄 ----------------------------------------III
表目錄 ----------------------------------------XII
附圖目錄 ---------------------------------------XIII
附表目錄 -----------------------------------------XV
第一章 緒論 ---------------------------------------1
第二章 金屬-有機材料化合物開發--------------------14
2.1 實驗儀器 -------------------------------------14
2.2 藥品來源 -------------------------------------15
2.3 合成步驟 -------------------------------------16
2.4 X光單晶繞射實驗及構造解析 --------------------24
第三章 結果與討論 --------------------------------38
3.1 (NH2Me2)[CuIdtp] (1) -------------------------38
3.2 (NH2Me2)4[Cudtp2Cl2] (2) ---------------------46
3.3 (NH2Me2)4[Mndtp2Cl2] (3) ---------------------53
3.4 (NH2Me2)3[In(TATAB)2]．2DMF (4) --------------60
3.5 (NH2Me2)3[In3(TATAB)4]．3DMF．20H2O (5) ------68
3.6 [Cu3(TATAB)2(H2O)3] (6) ----------------------79
第四章 結論 --------------------------------------90
參考文獻 -----------------------------------------91
附圖 ---------------------------------------------95
附表 --------------------------------------------111

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