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研究生： 林世民
Shih-ming Lin
論文名稱： 三核與四核錸金屬環錯合物之自組裝合成，
Self-assembly synthesis and molecular recognition of tripodal and tetrapodal rhenium-based discrete molecular architectures
指導教授： 呂光烈
Kuang-lieh Lu
口試委員:
學位類別： 碩士
Master
系所名稱： 理學院 - 化學學系
Department of Chemistry
畢業學年度： 95
語文別： 中文
論文頁數： 135
中文關鍵詞： 錸金屬 、金屬環化錯合物 、超分子 、自組裝
外文關鍵詞： rhenium-based, macrocycles, supermolecular, self-assembly
相關次數： 點閱：12  下載：0 
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    • 本論文首先合成兩個三邊鉗合型有機配子(1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene (L1)、 1,3,5-tris(5,6-dimethylbenzimidazol-1-ylmethyl) -2,4,6-trimethylbenzene (L2)及一個四邊鉗合型有機配子1,2,4,5-tetrakis(5,6-dimethybenzimidazol-1-ylmethyl)benzene (L3)，產率極高。接著利用這些三邊或四邊鉗合型配子和剛性螯合有機配子與Re2(CO)10進行水熱法自組裝得到一系列特殊結構之錸金屬單體超分子: [{Re(CO)3}3 (µ-BzIm)3(µ-L1)] (1)、[{Re(CO)3}3 (µ-Im)3(µ-L1)] (2)、[[{Re(CO)3}2(μ-Q)](μ3-L1){Re(CO)3(HQ)}．C7H8．C8H10] (3)、[[{Re(CO)3}2(μ-Q)](μ3-L2){Re(CO)3(HQ)}．2C9H12] (4)、[[{Re(CO)3}4(μ-2-(2-pyridyl)-benzimidazol]2(μ4-L3)] (5)、[[{Re(CO)3}4(μ-2-(2-pyridyl)-benzimidazol]2(μ4-L3) ．2C9H12] (5'')，(BzIm = benzoimidazole，Im = imidazole， Q = 6,11-dihydroxy-5,12-naphthacenedione)。產物結構經由元素分析、FAB-MS、IR與NMR儀器鑑定，並進一步經單晶X射線繞射解析。晶體結構分析顯示化合物1、2由三個fac-Re(CO)3為超分子化合物之邊角，以順式構形有機配子L1與imidazolyl配位基作為連接，形成具有三邊旋轉對稱的三核密閉籠狀結構。化合物3、4 由三個fac-Re(CO)3 、naphthacenedione與反式構形有機配子L1、L2組裝成三核開放豬籠草結構。化合物5、5''由四個fac-Re(CO)3、一個順、反、順、反有機配子L3與不對稱的三個氮配位基2-(2-pyridyl)-benzimidazol組裝成類似分子夾的結構。本論文金屬嵌入環化錯合物皆利用1H NMR和FAB-MS法鑑定結構。

    Two angular tripodal ligands (1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethylbenzene (L1), 1,3,5-tris(5,6-dimethylbenzimidazol-1-ylmethyl) -2,4,6-trimethylbenzene (L2) and one tetrapodal ligand 1,2,4,5-tetrakis(5,6-dimethybenzimidazol-1-ylmethyl)benzene (L3) were synthesized in high yields. Reactions of Re2(CO)10 with these shape-specific ligands L and other chelate ligands under hydrothermal conditions afforded a series of rhenium-based discrete molecular architectures: [{Re(CO)3}3 (µ-BzIm)3(µ-L1)] (1), [{Re(CO)3}3 (µ-Im)3(µ-L1)] (2), [[{Re(CO)3}2(μ-Q)](μ3-L1){Re(CO)3(HQ)}．C7H8．C8H10] (3), [[{Re(CO)3}2(μ-Q)](μ3-L2){Re(CO)3(HQ)}．2C9H12] (4), [[{Re(CO)3}4(μ-2-(2-pyridyl)-benzimidazol]2(μ4-L3)] (5), [[{Re(CO)3}4(μ-2-(2-pyridyl)-benzimidazol]2(μ4-L3) ．2C9H12] (5''), BzIm = benzoimidazole, Im = imidazole, Q = 6,11-dihydroxy-5,12-naphthacenedione. The products were characterized by elemental analysis, FAB-MS, IR, and NMR spectroscopies, and their structures were further comfirmed by X-ray crystallography. Compounds 1 and 2 adopt trigonal-closed cage structure with a 3-fold rotational symmetry in which three corner fac-Re(CO)3 moieties are connected by a sym-conformational L1 ligand and imidazolyl ligands. Compounds 3 and 4 consist of trigonal-open structure assembled from three fac-Re(CO)3 moieties, a naphthacenedione ligand and a anti-conformational L1 or L2 ligand. The structures of 5 and 5'' are tetragonal molecular clips constructed by four fac-Re(CO)3 moieties, which are linked by a cis, trans, cis, trans-conformational L3 ligand and a non-symmetry 3N ligand. The 1H NMR spectrometry and FAB-MS spectroscopy were utilized to elucidate the solution structures of these macrocycles.

    中文摘要 I 英文摘要 II 致謝 III 目錄 IV 圖目錄 V 表目錄 X 第一章　序論 1 第一節　金屬嵌入環化錯合物（metallacycle） 1 第二節　可動性基團（flexible motif） 2 第三節　溶劑模板（solvent-templated）通道結構 3 第四節　臭味檢測 5 第二章　研究動機 7 第三章　實驗部份 10 第一節　儀器及藥品 10 第二節　有機配子合成 13 第三節　錸金屬超分子之合成 19 第四章　結果與討論 28 第一節 合成策略 29 第二節 合成方法的探討及金屬化合物的光譜鑑定 32 第三節 化合物結構及物性探討 48 第四節 化合物之光物理探討 73 第五章　結論 77 參考文獻 78 附錄 82

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