含N-(2-嘧啶)甲醯胺配位基與一價銀及二價銅化合物之合成,結構與特性研究

Synthesis, structures and properties of Silver (I) and Copper (II) Complexes Containing N-(2-pyrimidinyl)formamide Ligand

郭盈孜(Ying-Tzu Kuo)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2009年)

https://doi.org/10.6840/cycu200900795

摘要

本論文主要討論含 N-(2-嘧啶)甲醯胺配位基(L)與過渡金屬一價銀和二價銅之化學。將配位基與分別與過渡金屬化合物 AgX (X ＝ ClO4－，BF4－，SO3CF3－，SbF6－) 以及 Cu(BF4)2 • 6H2O、Cu(ClO4)2 • 6H2O、CuCl2反應，可得到一維高分子鏈 {[Ag(L)](ClO4)}∞，1； {[Ag(L)](BF4)}∞，2 和 [Ag(L)(SO3CF3)]∞，3，零維單核化合物 [Ag(L)2](SbF6)，4；Cu(L)2(BF4)2，5；Cu(L)2(ClO4)2，6 和Cu(L)Cl2，7，以上七種化合物均可以利用元素分析儀、紅外光光譜儀和熱重分析儀鑑定之。而單晶結構均以單晶 X-ray 繞射儀鑑定之。高分子鏈 1 和 2 中, 主要藉由陰離子的 Ag---O 及Ag---F 作用力及芳香環間π – π作用力將高分子鏈形成三維超分子結構。化合物 3，中心金屬銀形成四配位獨特的扭曲三角錐構型，其高分子鏈間經由 Ag---O 及 F---F 作用力在空間中進行堆疊延伸，形成具有孔道的三維超分子架構。在化合物 4 中，分子內具有特殊的 C-H---Ag 弱作用力，分子間更透過 Ag---F、Ag---O 和氫鍵作用力堆疊形成三維超分子結構。在化合物5和6中，因為分子間的兩組自互補氫鍵 C-H---X，N-H---X (X = O or F) 存在，將分子連結成二維的層狀結構。化合物7，中心金屬銅的構型是一個扭曲的四邊形，分子間透過 C-H---Cl 和 N-H---Cl 氫鍵，形成了一維鏈具有波浪狀的結構。

關鍵字

單晶結構 ； 銀金屬 ； 銅金屬

並列摘要

This thesis discusses the chemistry of silver(I) and copper(II) complexes containing N-(2-pyrimidinyl) formamide (L). The reactions of ligand L with AgX (X ＝ ClO4－, BF4－, SO3CF3－, SbF6－) and Cu(BF4)2 • 6H2O, Cu(ClO4)2 • 6H2O, CuCl2 afforded the 1-D polymeric chains {[Ag(L)](ClO4)}∞, 1, {[Ag(L)](BF4)}∞, 2 and [Ag(L)(SO3CF3)]∞, 3, and the 0-D monomeric complexes [Ag(L)2](SbF6), 4, Cu(L)2(BF4)2, 5, Cu(L)2(ClO4)2, 6 and Cu(L)Cl2, 7. All the complexes have been characterized by EA, IR spectroscopic and TGA methods and structurally characterized by X-ray crystallography. The polymeric chains of 1 and 2 are linked by the anions through Ag---O and Ag---F, and π – π stacking interaction to form a 3-D supramolecular structure. The silver centers in complex 3 form the four coordinated, distorted trigonal pyramidal geometry, and each polymeric chains are linked through Ag---O and F---F interactions, which further extend into a 3-D supramolecular frameworks with channels. Complexes 4 shows a C-H---Ag intramolecular hydrogen bonding, and the molecules pack into a 3-D supramolecular framework through intermolecular Ag---F and Ag---O interactions and hydrogen bonds among mononuclear cationic units and anions. In complexes 5 and 6, a set of interactions involving two self-complementary double C-H---X and N-H---X (X = O or F) hydrogen bonds between molecules were found to link the molecules to form 2-D layers. The Cu centers in complex 7 form a distorted square planar geometry, and its molecules are linked through C-H---Cl and N-H---Cl hydrogen bonds to form a 1-D wave-like chain.

並列關鍵字

X-ray crystallography ； copper ； silver

參考文獻

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