Department of Chemistry, Zhengzhou University, Zhengzhou, 450001, PR China.
Dalton Trans. 2011 Oct 21;40(39):10071-81. doi: 10.1039/c1dt10830a. Epub 2011 Sep 2.
The reactions of 1,2,3,4-benzenetetracarboxylic acid (H(4)mpda) and different silver(I) salts under hydrothermal or solvent evaporation conditions yielded four unusual coordination complexes with interesting frameworks: Ag(4)(mpda) (1), {[Ag(2.5)(mpda)(bpy)(2)]·[Ag(bpy)]·[Ag(bpy)(H(2)O)]·(NO(3))(0.5)·(H(2)O)(9)}(n) (2), {[Ag(5)(mpda)(2)(bpy)(4)]·[Ag(bpy)]·[Ag(bpy)(H(2)O)]·[Ag(bpy)(H(2)O)]·(H(2)O)(16)}(n) (3), {[Ag(2)(mpda)(H(2)O)]·[Ag(bpy)]·[Ag(bpy)]}(n) (4) (bpy = 4,4'-bipyridine). Complex 1 displays a novel (3,4,7)-connected {4.6(2)}{4.6(5)}{4(2).6(13).8(5).10} topology, in which the carboxylic groups of the mpda(4-) ligand adopt variable coordination modes. In 1, besides Ag-O coordination bonding, AgAg and Agaromatic intermolecular interactions also make their appearance. In complexes 2-4, rare architectures comprising three or four isolated coordination polymers within the same crystalline structure have been obtained, respectively. In 2 and 3, neighboring layers are linked together through water tapes into a three-dimensional supramolecular architecture, which is also consolidated by π···π stacking, while independent infinite rod-like polymer chains fill the void space between layers. Interestingly, an anionic (H(2)O-NO(3)(-))(n) layer, built from water tapes and nitrate anions as well as consolidated by the mpda(4-) ligands, has been structurally identified in compound 2. A new water tape constructed from alternating tetramers and decamers has been obtained in compound 3. In compound 4, a right-handed helical chain and two rod-like polymeric chains are interconnected through host-guest molecular recognition to generate a three-dimensional chiral supramolecular architecture. Bulk materials for 1 and 4 have second-harmonic generation activity, being approximately 0.6 and 0.4 times that of urea. The IR spectra, thermogravimetric analysis and luminescent properties of all compounds were also investigated.
1,2,3,4-苯四羧酸（H(4)mpda）与不同的银（I）盐在水热或溶剂蒸发条件下反应，生成了四个具有有趣骨架的不寻常配位化合物：Ag(4)(mpda)（1），{[Ag(2.5)(mpda)(bpy)(2)]·[Ag(bpy)]·[Ag(bpy)(H(2)O)]·(NO(3))(0.5)·(H(2)O)(9)}(n)（2），{[Ag(5)(mpda)(2)(bpy)(4)]·[Ag(bpy)]·[Ag(bpy)(H(2)O)]·[Ag(bpy)(H(2)O)]·(H(2)O)(16)}(n)（3），{[Ag(2)(mpda)(H(2)O)]·[Ag(bpy)]·[Ag(bpy)]}(n)（4）（bpy = 4,4'-联吡啶）。 配合物 1 显示出一种新颖的（3,4,7）连接的{4.6(2)}{4.6(5)}{4(2).6(13).8(5).10}拓扑结构，其中mpda(4-)配体的羧酸基团采用可变的配位模式。在 1 中，除了 Ag-O 配位键外，AgAg 和 Agaromatic 分子间相互作用也同时存在。在配合物 2-4 中，分别得到了包含三个或四个孤立配位聚合物的罕见结构。在 2 和 3 中，相邻的层通过水带连接成一个三维超分子结构，这也通过π···π堆积得到加强，而独立的无限棒状聚合物链填充在层之间的空隙中。有趣的是，在化合物 2 中，结构上确定了一个由水带、硝酸盐阴离子以及由 mpda(4-)配体构成的阴离子（H(2)O-NO(3)(-))(n)层。在化合物 3 中，获得了一种由交替的四聚体和十聚体构成的新的水带。在化合物 4 中，一个右手螺旋链和两个棒状聚合物链通过主体-客体分子识别相互连接，生成一个三维手性超分子结构。1 和 4 的块状材料具有二次谐波产生活性，大约是尿素的 0.6 和 0.4 倍。还研究了所有化合物的红外光谱、热重分析和发光性质。
