研究生: |
曾宜秀 |
---|---|
論文名稱: |
碳-氫鍵活化合成錸金屬環錯合物及其分子辨識研究 Preparation of Rhenium-Based Metallacycles via C-H Bond Activation and Their Molecular Recognition Capabilities |
指導教授: |
許貫中
Hsu, Kung-Chung 呂光烈 Lu, Kuang-Lieh |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2008 |
畢業學年度: | 96 |
語文別: | 中文 |
論文頁數: | 160 |
中文關鍵詞: | 金屬環錯合物 、錸 、晶體結構 、分子辨識 、碳-氫鍵活化 |
英文關鍵詞: | metallacycle, rhenium, crystal structure, molecular recognition |
論文種類: | 學術論文 |
相關次數: | 點閱:181 下載:2 |
分享至: |
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本論文的研究是利用Re2(CO)10與2-(2-pyridyl)-benzimidazole (HBim-C6H4N)
及1,4-bis(benzimidazole-1-ylmethyl)-2,3,5,6-tetramethylbenzene (p-TXyBim, L1)、
α,α′-bis(benzimidazol-1-yl)-o-xylene (o-XyBim, L2) 、
1,3-bis(benzimidazole-1-ylmethyl)-2,4,6-trismethylbenzene (m-TXyBim, L3) 、
1,2-bis(4-pyridyl)ethane (bpea, L4)或1,3-bis(4-pyridyl)propane (bppa, L5)等有機配
子在水熱條件下自組裝合成,分別得到[{Re(CO)3(μ-Bim-C6H4N)}2(μ-L1)] (1)、
[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L2)] (2)、[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L3)] (3)、
[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L4)] (4)、[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L5)] (5)等錸
金屬錯合物。錯合物15經由UV-vis、IR、NMR、FAB-MS等方法鑑定,其結構
也以單晶X光繞射法解析。化合物1為一雙核非環狀錯合物,具發光特性,可藉
由可見-紫外光光譜上的差異來辨識Hg+、Cu2+及Ag+等三種金屬離子。化合物25
的結構為雙核金屬環化物,除了其光物理性質之外,該系列分子的特色是錸金屬
將有機配子2-(2-pyridyl)benzimidazole中3號位置(C3)的碳-氫鍵活化而形成雙核
環化物。
Compounds [{Re(CO)3(μ-Bim-C6H4N)}2(μ-L1)] (1),
[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L2)] (2), [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L3)] (3),
[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L4)] (4), and [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L5)] (5)
were successfully synthesized by treatment of Re2(CO)10 with
2-(2-pyridyl)-benzimidazole (HBim-C6H4N) and
1,4-bis(benzimidazole-1-ylmethyl)-2,3,5,6-tetramethylbenzene (p-TXyBim, L1),
α,α′-bis(benzimidazol-1-yl)-o-xylene (o-XyBim, L2),
1,3-bis(benzimidazole-1-ylmethyl)-2,4,6-trismethylbenzene (m-TXyBim, L3),
1,2-bis(4-pyridyl)ethane (bpea, L4), or 1,3-bis(4-pyridyl)propane (bppa, L5)
respectively, under solvothermal conditions. The series of rhenium-based complexes
15 was characterized using IR, UV-vis, and NMR spectroscopic techniques. The
structures were further confirmed by X-ray single-crystal diffraction analysis.
Compound 1 is a dimetallic complex with an acyclic conformation. Compound 1
exhibited luminescent properties. In addition, it recognized Hg+,Cu2+ and Ag+ ions
by means of discrimination on UV-vis spectra. Crystal structures showed that
compounds 25 possess dimetallic cyclic conformations. It is noteworthy that C-H
activation on 2-(2-pyridyl)benzimidazole occurred during preparation of these
metallacyclic compounds.
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