鈷、鎳、銅-咪唑超分子化合物之自組裝合成與結構分析

Self-assembly and structural analysis of Co, Ni, Cu-imidazole supramolecules

徐筱娟(Hsiao-Chuan Hsu)

指導教授 ： 曾添文

國立臺北科技大學/工程學院/化學工程所/碩士(2005年)

摘要

本論文利用含有咪唑 ( imidazole = Im ) 結構之 1,1’-carbonyldiimidazole及 1,1’-thiocarbonyldiimidazole 與金屬鹽類 ( Co、Ni、Cu ) 採用室溫擴散方式，進行自組裝合成金屬－咪唑系列超分子化合物。於固態時，它們都藉著分子間的氫鍵作用，引導每個單體自組裝¬而成三維結構。該化合物均經由X射線單晶繞射解析其晶體結構，並經元素分析 ( EA ) 測試鑑定其組織。
　　化合物[Ni(Im)6]∙(Cl)2∙4H2O (1)，Ni原子中心為六配位，鍵結六個咪唑基，咪唑上的氫和結晶水分子的氫，分別與氯離子以氫鍵連結；化合物[Ni(Im)4(H2O)2]∙(Cl)2 (2)，Ni原子為六配位，與四個咪唑基和兩個水分子配位鍵結，而水分子以對位方式排列，咪唑上的氫和配位水分子的氫，也分別與氯離子利用氫鍵鍵結；化合物 Cu(Im)4(NO3)2 (3)，Cu原子為六配位，配位子為四個咪唑基和兩個硝酸根，硝酸根亦採用對位方式排列，咪唑上的氫和硝酸根的的氧利用氫鍵相互鍵結；化合物 [Cu(Im)4Cl]∙Cl∙1/2H2O (4)，Cu原子中心為五配位，配位子為四個咪唑基和一個氯離子；化合物 [Co(Im)6]2∙(ClO4)4∙2(Im) (5)，Co原子中心為六配位，與六個咪唑基鍵結，周圍有兩個過氯酸根陰離子和一個自由咪唑基，彼此間亦以氫鍵的方式鍵結。由晶體解析數據可知化合物 1 與 5 屬三斜晶系；化合物 2 與 4 屬單斜晶系；而化合物 3 則屬斜方晶系。
　　以上所合成的化合物 1－5，除了以 X 射線單晶繞射解析其結構之外，也以X射線粉末繞射再次確認其結構，再以熱重損失 ( TGA ) 測試以探討其熱穩定性。

關鍵字

咪唑 ； 超分子 ； 自組裝 ； 氫鍵

並列摘要

Self-assembly of 1,1’-carbonyldiimidazole or 1,1’-thiocarbonyldiimidazole with metal (Co , Ni , Cu ) salts at room temperature led to the formation of a series of metal-imidazole supramolecules. Compounds 1 and 5 crystallize in a triclinic system, space group . Compounds 2 and 4 crystallize in a monoclinic system, space group C2/c and P21/n. Whereas compound 3 crystallizes in an orthorhombic system, space group Pna2. Their structures were characterized by spectroscopic methods and single-crystal X-ray diffraction analysis.
The structure of compound [Ni(Im)6]∙(Cl)2∙4H2O (1) shows that the Ni metal center is coordinated by six imidazole ligands. Hydrogen bonding interactions appear among the imidazole, the guest water molecules and the chloride ion. The ORTEP diagram of compound [Ni(Im)4(H2O)2]∙(Cl)2 (2) shows that the Ni center is coordinated with four imidazole ligands and two water molecules. The coordinated imidazole and the coordinated water molecules interact with chloride ions via hydrogen bonding. A X-ray diffraction analysis of compound Cu(Im)4(NO3)2 (3) reveals that the Cu metal center also adopts an octahedral geometry, which is bound to four imidazole ligands and two nitrate ions. The hydrogen atom of the coordinated imidazole interacts with the oxygen atom of a nitrate ion through hydrogen bonding. The structure of compound [Cu(Im)4Cl]∙Cl∙1/2H2O (4) is of particular interest. The Cu metal center is coordinated with four imidazole ligands and a chloride ion, forming a square-pyramidal geometry.
The structure of compound [Co(Im)6]2∙(ClO4)4∙2(Im) (5) is similar to that of 1. However, this species contains two guest imidazole molecules and four guest ClO4- ions.
　　The synthesized compounds 1－5 were also characterized by powder X-ray diffraction analysis and their stabilities in the solid state were examined by TGA technique.

並列關鍵字

imidazole ； supramolecules ； self-assemble ； hydrogen bonding

參考文獻

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