Liu Hai-Yan, Wu Hua, Ma Jian-Fang, Song Shu-Yan, Yang Jin, Liu Ying-Ying, Su Zhong-Min
Key Lab for Polyoxometalate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China.
Inorg Chem. 2007 Sep 3;46(18):7299-311. doi: 10.1021/ic070147s. Epub 2007 Aug 8.
In this Article, 11 silver complexes, namely, [Ag(L1)(2-Pyr)(H2O)] (1), Ag(L1)(2,3-Pyr) (2), [Ag2(L1)2(2Et,3Me-Pyr)2(H2O)] (3), Ag(2,6-Pyr).1.5H2O (4), Ag(L1)(2,5-Pyr) (5), Ag(H2O)2.H2O (6), [Ag(L2)(2-Pyr)] (7), [Ag(L2)(2,3-Pyr)].1.5H2O (8), [Ag(L2)(2Et,3Me-Pyr)].2H2O (9), Ag2(L2)(2,6-Pyr)(H2O)2.H2O (10) and [Ag(L2)(2,5-Pyr)].H2O (11) (2-Pyr=2-methylpyrazine; 2,3-Pyr=2,3-dimethylpyrazine; 2Et,3Me-Pyr=2-ethyl-3-methylpyrazine; 2,6-Pyr=2,6-dimethylpyrazine; 2,5-Pyr=2,5-dimethylpyrazine; L1=p-aminobenzenesulfonate anion and L2=6-amino-1-naphthalenesulfonate anion), have been synthesized and characterized by elemental analyses, IR spectroscopy, and X-ray crystallography. In 1, 3, and 4, Ag(I) centers are linked by bridging pyrazine ligands to form one-dimensional chains, whereas compound 2 shows a double-chain structure through weak Ag-C interactions. The structure analyses show that both 5 and 11 form two-dimensional networks composed of 26-membered metallocycles. Unexpectedly, compounds 6 and 10 show discrete structures. In compound 7, silver(I) centers are bridged by sulfonate anions to form a polymeric helical structure, and the 2-Pyr molecule acts as a monodentate ligand. Compounds 8 and 9 show hinged chain structures containing 14-membered rings, and these chains interlace with each other to generate unique three-dimensional structures. These results indicate that the substituting groups and the substituting sites of pyrazine derivatives play an important role in the framework formation of silver complexes. Additionally, the luminescent properties of these compounds are also discussed.
在本文中,已合成了11种银配合物,即[Ag(L1)(2 - Pyr)(H₂O)] (1)、Ag(L1)(2,3 - Pyr) (2)、[Ag₂(L1)₂(2Et,3Me - Pyr)₂(H₂O)] (3)、Ag(2,6 - Pyr)·1.5H₂O (4)、Ag(L1)(2,5 - Pyr) (5)、Ag(H₂O)₂·H₂O (6)、[Ag(L2)(2 - Pyr)] (7)、[Ag(L2)(2,3 - Pyr)]·1.5H₂O (8)、[Ag(L2)(2Et,3Me - Pyr)]·2H₂O (9)、Ag₂(L2)(2,6 - Pyr)(H₂O)₂·H₂O (10)和[Ag(L2)(2,5 - Pyr)]·H₂O (11)(2 - Pyr = 2 - 甲基吡嗪;2,3 - Pyr = 2,3 - 二甲基吡嗪;2Et,3Me - Pyr = 2 - 乙基 - 3 - 甲基吡嗪;2,6 - Pyr = 2,6 - 二甲基吡嗪;2,5 - Pyr = 2,5 - 二甲基吡嗪;L1 = 对氨基苯磺酸根阴离子,L2 = 6 - 氨基 - 1 - 萘磺酸根阴离子),并通过元素分析、红外光谱和X射线晶体学对其进行了表征。在1、3和4中,Ag(I)中心通过桥连的吡嗪配体连接形成一维链,而化合物2通过弱的Ag - C相互作用呈现双链结构。结构分析表明,5和11均形成由26元金属环组成的二维网络。出乎意料的是,化合物6和10呈现离散结构。在化合物7中,银(I)中心由磺酸根阴离子桥连形成聚合物螺旋结构,并且2 - Pyr分子作为单齿配体。化合物8和9呈现包含14元环的铰链链结构,并且这些链相互交织形成独特的三维结构。这些结果表明吡嗪衍生物的取代基和取代位点在银配合物的骨架形成中起重要作用。此外,还讨论了这些化合物的发光性质。