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    Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/6305

    Title: 三核與四核錸金屬環錯合物之自組裝合成, 結構鑑定與分子辨識研究;Self-assembly synthesis and molecular recognition of tripodal and tetrapodal rhenium-based discrete molecular architectures
    Authors: 林世民;Shih-ming Lin
    Contributors: 化學研究所
    Keywords: 錸金屬;金屬環化錯合物;超分子;自組裝;rhenium-based;macrocycles;supermolecular;self-assembly
    Date: 2007-06-12
    Issue Date: 2009-09-22 10:17:17 (UTC+8)
    Publisher: 國立中央大學圖書館
    Abstract: 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.
    Appears in Collections:[化學研究所] 博碩士論文

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