含甲咪配位基之多核銅金屬化合物與配位高分子之研究

Chemistry of Polynuclear Copper(I) Complexes and Coordination Polymers Supported by Formamidine & Formamidinate Ligands

林玹州(Hsuan-Chou Lin)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2015年)

https://doi.org/10.6840/cycu201500585

摘要

本論文主要探討含甲咪配位基之多核金屬化合物與配位高分子的結構與特性。
以起始物 3-aminopyridine、4-chloroaniline、4-bromoaniline或4-iodoaniline 和 triethylorthoformate 與一價鹵素銅CuX (X = Cl–，Br– 與I–)在不同的溶劑下以一步水熱合成法反應得到化合物[Cu3(3-pyf)2Cl3]n，1、[Cu4(3-pyf)4Br4],，2、[Cu(3-pyf)I]n，3、[Cu2(4-cphf)2]，7、[Cu2(4-Hbphf)4Br2]，8、[Cu2(4-iphf)2]，10、[Cu2(2-cpf)2]，11。若以3-aminopyridine和triethylortotformate、一價氯化銅和氫氧化鈉分別在甲醇、四氫呋喃和乙腈下反應，可得到化合物[Cu4(3-pyf)4]，4、化合物{[Cu8(3-pyf)8]·5THF}，5 以及化合物[Cu(3-pyf)]n，6。以4-bromoaniline和triethylorthoformate與一價溴化銅，同樣加入氫氧化鈉並於四氫呋喃下反應，可以得到[Cu2(4-bphf)2]，9。化合物1為三維的配位高分子，並具有(62.82.102)(62.8)2 - sur; bbf-3,4-Ccm的拓譜學結構，化合物2是一個四核銅金屬的水車結構，是非常罕見的零維結構。化合物3是一維的配位高分子，化合物4是一個四核銅，化合物5則為第一個具有銅-銅作用力的八核銅金屬之甲咪配位基錯合物，化合物6是一個二維的配位高分子，其拓譜學結構為{44.62}。化合物7, 9-11皆為雙核銅結構的零維化合物，而化合物8則是含有長斜方形Cu2Br2建構單元的雙核零維化合物。

關鍵字

配位高分子 ； 甲咪配位基 ； 一價銅鹵素

並列摘要

This thesis discusses the structures and properties of polynuclear copper(I) complexes and coordination polymers supported by formamidine and formamidinate ligands.
One-pot solvothermal reactions of 3-aminopyridine, 4-chloroaniline, 4-bromoaniline, 4-iodoaniline, or 4-amino-2-chloropyridine with triethylorthoformate and CuX (X = Cl–, Br– , I–) afforded complexes [Cu3(3-pyf)2Cl3]n, 1, [Cu4(3-pyf)4Br4], 2, [Cu(3-pyf)I]n, 3, [Cu2(4-cphf)2], 7, [Cu(4-Hbphf)4Br2], 8 , [Cu2(4-iphf)2], 10 and [Cu2(2-cpf)2], 11, whereas the reactions of CuX (X = Cl–, Br–) with 3-aminopyridine and 4-bromoaniline, in a Methanol (MeOH) or tetrahydrofuran (THF) or acetonitrile (ACN) solution containing triethylorthoformate and sodium hydroxide gave complexes [Cu4(3-pyf)4], 4, {[Cu8(3-pyf)8]·5THF}, 5, [Cu(3-pyf)]n, 6, and[Cu2(4-bphf)2], 9, which were characterized by X-ray crystallography. Complex 1 is a 3D coordination polymer with (62.82.102)(62.8)2 - sur; bbf-3,4-Ccm topology, complex 2 is a very rare example of tetranuclear paddlewheel complex containing rhombohedral Cu2X2, complex 3 is a 1D chain structure, complex 4 is a tetranuclear complex with cuprophilicity, complex 5 is the first octanuclear complex with Cu(I)---Cu(I) interactions, complex 6 is a 2D structure of {44.62} topology, complexes 7, 9–11 are dinuclear copper(I) complexes that shows different distances of Cu(I)---Cu(I), and complex 8 is a dinuclear complex containing rhombohedral Cu2Br2 unit.

並列關鍵字

Coordination polymer ； formamidine ligand ； Copper(I) halide

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