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氨基吡啶衍生物控制了Cu-BTC金属有机框架的组装及各种性质。

Aminopyridine derivatives controlled the assembly and various properties of Cu-BTC metal-organic frameworks.

作者信息

Wang Xiuli, Le Mao, Lin Hongyan, Luan Jian, Liu Guocheng, Liu Danna

机构信息

Department of Chemistry, Bohai University, Jinzhou, 121000, P. R. China.

出版信息

Dalton Trans. 2015 Aug 21;44(31):14008-18. doi: 10.1039/c5dt01446h.

Abstract

Three Cu(ii) metal-organic frameworks (MOFs) based on 1,3,5-benzenetricarboxylic acid (H3BTC) and three aminopyridine derivatives with different lengths and coordination groups, namely [Cu2(3-azpy)(HBTC)(H2BTC)(μ3-OH)(H2O)2] (), [Cu2(3-ppca)(BTC)(H2O)3]·H2O (), [Cu2(3-ebpba)(BTC)(μ3-OH)] () [3-azpy = 3,3'-azopyridine, 3-ppca = N-(pyridin-3-yl)pyrazine-2-carboxamide, 3-ebpba = (E)-4,4'-(ethene-1,2-diyl)bis(N-pyridin-3-yl)benzamide)], have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, PXRD, TG and single crystal X-ray diffraction analyses. The title MOFs display versatile structural features with 2D and 3D frameworks. Complex exhibits a 2D layer, which is constructed from the 3-azpy bridging ligands and a 1D ladder-like Cu-BTC chain with tetranuclear copper clusters. The 3-azpy was in situ transformed from 3-aminopyridine under the hydrothermal conditions. Complex shows a rare 3D framework, which features a (3,3,3,3)-connected topology with a Schläfli symbol of {8·10·12}2{8(2)·10}2. Complex exhibits a (3,8)-connected {4·6(2)}2{4(2)·6(22)·7·8(3)} topology based on tetranuclear copper clusters. The influence of aminopyridine-based ligands on the structures and properties of the title complexes has been discussed. The electrocatalytic and photocatalytic properties of complexes have also been investigated in detail.

摘要

基于1,3,5-苯三甲酸(H3BTC)和三种具有不同长度和配位基团的氨基吡啶衍生物,水热合成了三种铜(II)金属有机框架(MOF),即[Cu2(3-azpy)(HBTC)(H2BTC)(μ3-OH)(H2O)2]()、[Cu2(3-ppca)(BTC)(H2O)3]·H2O()、[Cu2(3-ebpba)(BTC)(μ3-OH)]()[3-azpy = 3,3'-偶氮吡啶,3-ppca = N-(吡啶-3-基)吡嗪-2-甲酰胺,3-ebpba = (E)-4,4'-(乙烯-1,2-二基)双(N-吡啶-3-基)苯甲酰胺],并通过元素分析、红外光谱、粉末X射线衍射、热重分析和单晶X射线衍射分析对其进行了结构表征。标题中的MOF具有二维和三维框架的多种结构特征。配合物呈现二维层状结构,由3-azpy桥连配体和具有四核铜簇的一维梯状Cu-BTC链构成。3-azpy在水热条件下由3-氨基吡啶原位转化而来。配合物呈现罕见的三维框架结构,其具有(3,3,3,3)连接的拓扑结构,Schläfli符号为{8·10·12}2{8(2)·10}2。配合物基于四核铜簇呈现(3,8)连接的{4·6(2)}2{4(2)·6(22)·7·8(3)}拓扑结构。讨论了基于氨基吡啶的配体对标题配合物结构和性质的影响。还详细研究了配合物的电催化和光催化性质。

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