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研究生: 鄭堯文
Cheng, Yao-Wen
論文名稱: 含3-(2'-吡啶基)-1,2,4-三氮唑衍生物之錸金屬錯合物:合成、光物理性質及其陰離子感測研究
Studies of the synthesis, photophysical properties, and anion sensing behaviors with Re(I)-tricarbonyl complexes containing 3-(2'-Pyridyl)-1,2,4-triazole ligand
指導教授: 孫世勝
Sun, Shih-Sheng
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2013
畢業學年度: 101
語文別: 中文
論文頁數: 149
中文關鍵詞: 陰離子感測器錸金屬錯合物1,2,4-三氮唑氫鍵作用藍位移
英文關鍵詞: anion sensors, rhenium(I) complexes, 1,2,4-triazole, hydrogen bonding interaction, hypsochromic shift
論文種類: 學術論文
相關次數: 點閱:138下載:1
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  • 本論文主要探討兩個含有 3-(2'-吡啶基)-1,2,4-三氮唑配位子之錸金屬錯合物之陰離子感測行為,並且經由核磁共振光譜、高解析質譜分析及單晶結構繞射進行純度及結構鑑定,發現由於三氮唑配位子能以不同位置的氮原子進行配位反應,因此所得之錯合物 DL25-A 與 DL25-B 為結構異構物。並且在乙腈溶劑中,經由紫外光-可見光吸收、放光及核磁共振等滴定實驗,對其進行陰離子感應測試;由測試結果得知,當陰離子加入時其吸收及放光光譜皆會呈現藍位移的變化趨勢,並且由核磁共振光譜證實,兩者皆進行去質子化的作用機制。
      除此之外,我們以菸醯苯胺(Nicotinanilide)對錯合物 DL25-A 及DL25-B 上的溴原子進行取代,發現其所得產物皆為 DL75,並且藉由晶體結構推測,DL25-A在反應過程中,會因周圍溶劑分子進行配位而導致結構產生重組。

    Two rhenium(I) tricarbonyl complexes with 3-(2'-pyridyl)-1,2,4-triazole chelating ligand for anion sensing has been designed and synthesized. The identity and purity of these complexes have been characterized by NMR spectroscopy, mass spectrometry, and X-ray single-crystal diffraction. The complexes DL25-A and DL25-B are isomers to each other with the triazole ligand coordinating to Re(I) in different N-atoms. The anion sensing properties have been evaluated by UV-vis absorption, fluorescence, and 1H NMR titration experiments in acetonitrile. The absorption and fluorescence spectra for both complexes showed hypsochromic shifts upon addition of anions. The results of 1H NMR titration experiments have been confirmed that anion-receptor interaction is simple anion-induced deprotonation process.
      In addition, the same product, DL-75, was obtained upon replacing the Br atom on the complex DL25-A and DL25-B with nicotinanilide, which was confirmed by the crystal structure analysis. A structural re-orientation upon formation of the solvato-intermediate has been proposed to rationalize the reaction mechanism.

    中文摘要 I 英文摘要 II 目錄 III 圖目錄 V 表目錄 X 附錄 XII 一、緒論 1 1-1 陰離子對人類與環境的影響 1 1-2 超分子化學 2 1-3 感測器(sensor) 2 1-4 陰離子感測器之設計 4 (1) 幾何形狀 5 (2) 靜電作用效應 5 (3) 溶劑環境對陰離子的影響 6 (4) 疏水性程度 6 1-5 感測器與陰離子之作用行為 7 (1) 靜電作用力 7 (2) 氫鍵作用力 8 (3) 靜電作用力與氫鍵作用力  11 (4) 路易士酸鹼作用力 12 (5) 疏水性效應 13 1-6 陰離子化學感測器 14 (1) 以電化學作偵測 14 (2) 以光學訊號作偵測 15 1-7 螢光光譜 16 (1) 光的激發與放射 16 (2) 光誘導電子轉移(Photoinduced electron transfer) 17 (3) 分子內部電荷轉移(Intramolecular charge transfer) 19 1-8 過渡金屬錯合物之離子感測器 22 1-9 含 1,2,4-三氮唑之金屬錯合物 26 1-10 研究動機 28 二、實驗部分 29 2-1 分析儀器 29 2-2 實驗藥品 32 2-3 實驗流程 33 2-4 實驗合成 36 三、結果與討論 50 3-1 錯合物 DL25-A、DL25-B 及 DL75 之基本光物理性質 50 3-2 錯合物 DL25-A 及 DL50 之單晶結構分析 52 3-3 錯合物對陰離子之感測行為實驗 57 3-3-1 錯合物 DL25-A 對陰離子感測行為實驗 57 3-3-2 錯合物 DL25-A 對陰離子之定量分析 58 3-3-3 錯合物 DL25-B 對陰離子感測行為實驗 70 3-3-4 錯合物 DL25-B 對陰離子之定量分析 71 3-3-5 錯合物 DL75 對陰離子感測行為實驗 86 3-3-6 錯合物 DL25-A 及 DL25-B 與陰離子之結合常數 87 四、結論 88 五、參考文獻 89 附錄 93

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