銀、錸長方形、三角形分子之自組裝合成，
結構與光物理特性研究

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姓名

蔡琪惠(Chi-Hwe Tsai) 查詢紙本館藏

畢業系所

化學學系

論文名稱

銀、錸長方形、三角形分子之自組裝合成，結構與光物理特性研究
(Self-Assembly, structure and photophysical properties of silver and Rhenium )

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摘要(中)

中文摘要
本論文研究重點在於以4,4’-bis(2-pyridylmethyleneamine)-3,3’- dimethylbiphenyl (BPDBP)及1,1’-carbonyldiimidazole當作有機配子，利用室溫自組裝或水熱法的合成方式，製備長方形、三角形金屬環狀分子或高分子配位聚合物。
利用BPDBP做為有機配子，與過渡金屬陽離子﹙Ag+和Cd2+﹚經室溫自組裝合成出化合物 [Ag2(BPDBP)2(NO3)](NO3) ∙ H2O (1)、[Ag2(BPDBP)2](SbF6)2 ∙ 2(C6H5NO2) (2)、[Ag2(BPDBP)2](ClO4)1.5(OH)0.5 ∙ 1.25H2O ∙ 0.25CH3OH (3)、[Cd2(BPDBP)2(ClO4)2] (4) 以及化合物 [Cd2(BPDBP)(NO3)2]n (5)，其中化合物1–4皆為長方形結構。化合物1中，兩個銀金屬中心分別為五配位的四方角錐﹙square pyramidal﹚和四配位的平面四方﹙square planar﹚的幾何構形；在化合物2和3中，銀金屬中心則皆為四配位的平面四方﹙square planar﹚。鎘金屬中心在化合物4中是六配位的八面體﹙octahedron﹚構形。固態結構分析顯示這些矩形分子結構皆具有分子內π–π作用力。化合物5是一維鋸齒狀結構，鎘金屬中心為八配位。
以1,1’-carbonyldiimidazole與Re2(CO)10利用水熱法合成出化合物[Re3(μ-C3H3N2)3(CO)12] (6)，為一個三角形錸金屬環狀分子。金屬中心為六配位的八面體﹙octahedron﹚構形，位於咪唑環對位的Re?CO 鍵長略短於其他的Re?CO鍵長。此外，此三角形環狀分子經過堆疊後，由於分子間的弱C−H∙∙∙O作用力而形成一維梯形﹙ladder-like chain﹚的穩定結構。
最後，長方形與三角形環狀分子都顯現發光的特性，具有發展成有機/無機奈米級發光材料的潛在應用性。

摘要(英)

Abstract
A series of discrete supramolecules and one coordination polymer were synthesized via the self-assembly strategy from 4,4’-bis(2-pyridylmeathyleneamine)-3,3’-dimethylbiphenyl (BPDBP) or 1,1’-carbonyldiimidazole with rhenium metal salts. The solid state structures of the products were characterized by single-crystal X-ray diffraction analyses.
Treatment of BPDBP with Ag+ and Cd2+ ions leads to the formation of a series of rectangular compounds [Ag2(BPDBP)2(NO3)](NO3) ∙ H2O (1), [Ag2(BPDBP)2](SbF6)2 ∙ 2(C6H5NO2) (2), [Ag2(BPDBP)2](ClO4)1.5(OH)0.5 ∙ 1.25H2O ∙ 0.25CH3OH (3), [Cd2(BPDBP)2(ClO4)2] (4), and an one dimensional species [Cd2(BPDBP)(NO3)2]n (5). Solid-state structure analysis reveals that compounds 1–4 adopt rectangular geometry with a M2L2 fashion. The two silver centers in 1 are crystallographically independent. The coordination environments around the two silver centers are five-coordinated square pyramidal and four-coordinated square planar geometries, respectively. Whereas both the two silver centers in 2 and 3 are four-coordinated square planar. In 4, the cadmium(II) centers are coordinated by four nitrogen atoms from two BPDBP ligands and two perchlorate ions to furnish an octahedron geometry. All these compounds show intramolecular π?π interactions between the two BPDBP ligands in stabilizing the rectangular structures. Compound 5 presents a one-dimensional zigzag chain architecture. The coordination number around Cd(II) ion is eight, which composes of four nitrogen atoms from two Schiff-bases and four oxygen atoms from two nitrate anions.
Reaction of Re2(CO)10 with 1,1’-carbonyldiimidazole in the presence of toluene under hydrothermal conditions gives compound [Re3(μ-C3H3N2)3(CO)12] (6). Each rhenium(I) center in 6 is six-coordinated octahedron consisting of four carbonyl groups and two nitrogen atoms. The Re–CO bonds trans to imidazolyl ligand are significant shorter than that of the other two groups. The packing diagram of 6 shows that the discrete triangular molecules are arranged in a one-dimensional ladder-like chain through weak intermolecular C–H∙∙∙O interactions.

關鍵字(中)

★ 結構
★ 自組裝

關鍵字(英)

★ self-assembly
★ structure

論文目次

中文摘要I
英文摘要III
圖目錄iii
表目錄vii
第一章序論1
1.1 奈米(nanometer)1
1.2 超分子化學4
1.3 自組裝(self-assembly method)10
1.4 水熱反應(hydrothermal reaction)18
1.5 研究動機20
1.6 金屬與有機配子的選擇22
第二章實驗部分24
2.1 儀器與藥品24
2.1.1 儀器25
2.1.2 藥品26
2.2 有機配位基之合成與鑑定28
2.3 金屬矩形超分子合成33
2.3.1 室溫自組裝合成製備34
2.4 金屬三角形超分子合成49
第三章結果與討論53
第四章結論97
參考文獻98
附錄101
原子位置和熱參數及鍵長與鍵角表101

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指導教授

呂光烈(Kuang-Lieh Lu)

審核日期

2005-6-16

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