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| 研究生： |
王志銘 Chih-Min Wang |
|---|---|
| 論文名稱： |
有機‐無機複合化合物之合成、結構與性質研究 Synthesis, Crystal Structures and Properties of Organic-Inorganic Hybrid Compounds |
| 指導教授： |
李光華
Kwang-Hwa Lii |
| 口試委員: | |
| 學位類別： |
博士 Doctor |
| 系所名稱： |
理學院 - 化學學系 Department of Chemistry |
| 畢業學年度： | 97 |
| 語文別： | 中文 |
| 論文頁數： | 260 |
| 中文關鍵詞： | 催化特性 、光致發光 、氟化物 、亞磷酸鹽 、磷酸鹽 、水熱合成 |
| 外文關鍵詞： | phosphates, catalytic properties., luminescence, fluorides, phosphites, hydrothermal method |
| 相關次數： | 點閱：10 下載：0 |
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本論文主要是利用水熱反應 (hydrothermal reactions) 來進行具有新穎結構之金屬化合物的合成。相較於過渡性元素在配位化學上的研究，鈾與鑭系金屬的探討顯然少了很多，而且，過去的研究結果也顯示，孔洞材料有許多有趣的結構及潛在的應用性質，因此，我們希望藉由控制不同的有機模版、無機或有機配位基在中溫水熱的反應條件下，合成更多具有特殊結構的金屬化合物並對其性質做深入的研究。我們依照原子種類的不同，將研究計畫分成了兩個系列。
第一個系列主要使用不同的有機模版、配位基或加入第二種的金屬元素來合成 15 個結構新穎的鈾金屬化合物：U-1是第一個在鈾金屬系統裡同時含有一維鏈狀和二維層狀無機的組成，且金屬鈾的價數又為四、六混價的化合物。U-2是首次利用不同種類的金屬及有機配位基來合成具有三維孔洞結構的化合物，且在結構裡有機分子同時扮演配位基和模版的角色。U-3是第一個經由草酸連接形成pillared layer結構的氟化鈾化合物。U-4和U-5是第一個含有有機模版的草酸-氟化鈾的例子，特別的是其具有相同的化學組成但草酸與鈾金屬間的配位排列結構卻截然不同（U-4：魚骨頭形式的排列；U-5：一般長方形的排列)。在氟化鈾的合成經驗下，我們也將研究領域擴展至鈾金屬磷酸鹽的系統，例如：U-6和U-7是新穎結構之混和銅、鈾金屬磷酸鹽的例子。其餘含鈾金屬化合物之結構皆置於附錄 A中。
第二個系列主要使用不同的有機分子來合成結構新穎的鑭系金屬磷酸鹽或亞磷酸鹽化合物。在此系統裡，我們合成了 19 個化合物，其結構都經由單晶 X-ray 繞射儀或粉末 X-ray 繞射儀鑑定。Ln-1系列化合物是第一個草酸－鑭系金屬亞磷酸鹽化合物；Ln-13系列化合物是利用有機模版、配位基合成具有三維 honeycomb 孔洞結構的磷酸鹽化合物。Ln-17系列化合物則是首次成功將新類型的有機配位基導入鑭系金屬亞磷酸鹽的例子。其中部分鑭系金屬化合物已經被證實可以發出發紅光、藍光、綠光及紅外光，同時 Gd 和 Yb 化合物也被證實可以作為有機反應裡Biginelli Reaction的催化劑。
In this thesis, our work mainly focuses on the synthesis of metal compounds with novel structures by a hydrothermal method. Compared with a large number of publications of transition-metal compounds, the research on the synthesis of novel uranium or lanthanide compounds is considerable less. At the same time, the past studies also show that uranium- and(or) lanthanide-bearing materials display many interesting structural chemistry and potential applications, therefore, we aim at synthesizing new metal compounds with various architectures by adjusting the ratio of reactant in a hydrothermal method and then characterize their properties, such as luminescence and catalytic properties. 34 compounds in this research are divided into two series based on metal centers.
The first series is to synthesize and characterize novel uranium-containing compounds by choosing appropriately organic templates or(and) ligands into fluoride or phosphate systems. U-1 is an organically templated mixed-valent uranium(IV)/uranium(VI) oxyfluoride with a hybrid network structure (1D + 2D). U-2 is the first example of a mixed-metal uranium oxyfluoride incorporating an organic ligand. Bimetallic compounds are highly interesting because the second metal provides the possibility of incorporating organic ligands into the extended structures. U-3 is a new uranium(IV) fluorooxalate, in which oxalate ligands show bisbidentate coordination to the U atoms acting as pillars between adjacent uranium fluoride layers to produce an extended 3D network. U-4 and U-5 are the first examples of organically templated uranium fluorooxalates. Both of them consist of anionic [U2F6(C2O4)3]4- layers separated by organic ammonium cations and lattice water molecules. The building units within the layers are connected in different ways, which are very likely directed by the organic templates. U-6 and U-7 are two mixed-metal uranium compounds with a pillared layer structure. The organic ligands coordinate to the Cu atoms within adjacent uranium/copper phosphate( or arsenate) layers to generate a pillared layer structure. The other uranium compounds are categorized in appendix A.
The second series focuses on synthesis, characterization, and properties of novel lanthanide phosphates or phosphates. The 12 compounds (Ln-1-Ln-12) are isostructural and feature a 3D architecture in which 2D layers of [Ln(H2O)(HPO3)]+ are pillared by oxalate ligands. The structures of four isostructural organically templated lanthanide oxalatophosphates (Ln-13-Ln-16) contain 2D layers of lanthanide oxalates which are linked by dihydrogen phosphate units and bismonodentate oxalate ligands to form 3D frameworks. The three isostructural lanthanide phosphates (Ln-17-Ln-19) are observed for the first time by using a multidentate organic ligand, which was never used in metal phosphate and(or) phosphite systems before. Some of those lanthanide-bearing materials display red, blue, green, and near-IR luminescence. At the same time, it is also proved that the Yb and Gd compounds are effective catalysts for the Biginelli reaction.
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