Influence of anionic sulfonate-containing and nitrogen-containing mixed-ligands on the structures of silver coordination polymers
作者:Hua Wu、Xian-Wu Dong、Jian-Fang Ma、Hai-Yan Liu、Jin Yang、Hong-Ye Bai
DOI:10.1039/b814942a
日期:——
In this article, a series of mixed-ligand Ag(I) coordination polymers, namely, Ag(L1)H2O (1), Ag2(hmt)2(L1)2 (2), [Ag(HL2)]H2O (3), [Ag(L2)(biim)][Ag(biim)] (4), [K5(L3)2][Ag(H2O)2] (5), [Ag2(L3)(3-iso)][Ag(3-iso)]5H2O (6), [Ag3(L3)(bipy)3(H2O)]6H2O (7), [Ag3(L3)(biim)3]H2O (8), and [Ag3(L3)(hmt)2(H2O)3]H2O (9) (where hmt = hexamethylenetetramine, bipy = 4,4′-bipyridine, biim = 1,1′-(1,4-butanediyl)-bis(imidazole), 3-iso = 3-methylisoquinoline, L1 = 2,5-dichloro-4-amino-benzenesulfonate anion, L2 = 2-nitroso-1-naphthol-4-sulfonate anion and L3 = 4-hydroxy-5-nitro-1,3-benzenedisulfonate anion), have been synthesized by varying the anionic sulfonate-containing ligands and nitrogen-containing secondary ligands. Compounds 2 and 4 were synthesized through their parent compounds 1 and 3, respectively, while 6–9 were obtained by their parent compound 5. Ag(I) centers of 1 are linked by L1 anions to generate a 1D polymeric chain, while Ag(I) centers of 2 are bridged by hmt ligands to form a 2D polymeric layer. In 3, Ag(I) centers are connected by L2 anions to yield a 1D double chain, whereas Ag(I) centers in 4 are joined by biim ligands and L2 anions, generating an unusual anionic chain and a cationic chain, respectively. In 5, Ag(I) centers are coordinated by water molecules, and K(I) cations are coordinated by L3 anions to form a pillared layered structure with inorganic layers and organic pillars. In 6, Ag(I) centers are coordinated by 3-iso ligands and L3 anions to generate a discrete molecular structure. In 7, bipy ligands bridge Ag(I) centers to give Ag–bipy chains, which are further linked by L3 anions to produce a 2D polymeric layer. In 8, Ag(I) centers are bridged by biim ligands to generate a 1D polymeric chain. In 9, the hmt ligands connect Ag(I) centers to give a binodal (3,4)-connected net with (63)(65.8)2 topology. These results indicate that anionic sulfonate-containing ligands and the nitrogen-containing secondary ligands play important roles in the structural formation of the Ag(I) complexes. Additionally, the luminescent properties, elemental analyses and IR spectroscopy of these compounds were also studied.
在本文中,合成了一系列混合配体的Ag(I)配位聚合物,即Ag(L1)H2O (1)、Ag2(hmt)2(L1)2 (2)、[Ag(HL2)]H2O (3)、[Ag(L2)(biim)][Ag(biim)] (4)、[K5(L3)2][Ag(H2O)2] (5)、[Ag2(L3)(3-iso)][Ag(3-iso)]·5H2O (6)、[Ag3(L3)(bipy)3(H2O)]·6H2O (7)、[Ag3(L3)(biim)3]·H2O (8)和[Ag3(L3)(hmt)2(H2O)3]·H2O (9)(其中hmt = 六甲基四胺,bipy = 4,4′-联吡啶,biim = 1,1′-(1,4-丁烷二基)-双(咪唑),3-iso = 3-甲基异喹啉,L1 = 2,5-二氯-4-氨基苯磺酸根阴离子,L2 = 2-亚硝基-1-萘醇-4-磺酸根阴离子,L3 = 4-羟基-5-硝基-1,3-苯二磺酸根阴离子),通过改变含磺酸根的阴离子配体和含氮的二级配体合成。化合物2和4分别通过其母体化合物1和3合成,而化合物6–9则通过其母体化合物5获得。化合物1中,Ag(I)中心通过L1阴离子连接,形成一维聚合物链;而在化合物2中,Ag(I)中心通过hmt配体桥接,形成二维聚合物层。在化合物3中,Ag(I)中心由L2阴离子连接,生成一维双链,而在化合物4中,Ag(I)中心由biim配体和L2阴离子连接,分别生成不寻常的阴离子链和阳离子链。在化合物5中,Ag(I)中心与水分子配位,K(I)阳离子与L3阴离子配位,形成一种带有无机层和有机柱的立柱结构。在化合物6中,Ag(I)中心与3-iso配体和L3阴离子配位,生成离散的分子结构。在化合物7中,bipy配体桥接Ag(I)中心,形成Ag–bipy链,这些链又通过L3阴离子进一步连接,产生二维聚合物层。在化合物8中,Ag(I)中心由biim配体桥接,生成一维聚合物链。在化合物9中,hmt配体连接Ag(I)中心,形成具有(63)(65.8)2拓扑结构的双节点(3,4)连接网。这些结果表明,含磺酸根的阴离子配体和含氮的二级配体在Ag(I)配合物的结构形成中起着重要作用。此外,还研究了这些化合物的发光性质、元素分析和红外光谱。