R-Isophthalate (R = –H, –NO2, and –COOH) as modular building blocks for mixed-ligand coordination polymers incorporated with a versatile connector 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole
R-Isophthalate (R = –H, –NO2, and –COOH) as modular building blocks for mixed-ligand coordination polymers incorporated with a versatile connector 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole
复制标题
DOI：
10.1039/b711447h
复制
发表时间：
2008-02
期刊：
影响因子：
3.1
通讯作者：
M. Du;Zhihui Zhang;Yan-Ping You;Xiao‐Jun Zhao
中科院分区：
文献类型：
--
作者：
M. Du;Zhihui Zhang;Yan-Ping You;Xiao‐Jun Zhao
以3，3‘-联吡啶为连接体4-氨基-3，5-二(3-吡啶)-1，2，4-三氮唑(3-BPT)，将苯二甲酸共配体由间苯二甲酸(H_2ip)改为5-取代的5-硝基-间苯二甲酸(-NO_2，H_2nip)和偏苯三甲酸(-COOH，H_3TMA)，合成了9种CoII，CuII和CdII混配配合物。所有化合物均经X-射线衍射法确定了结构。结果表明，除了单体离子对产物[Co(3-bpt)2(H2O)4]·(H_2tma)_2·(H_2O)_2(1c)外，大多数都是配位聚合物，其中苯羧酸的配体被双去质子化以补偿电荷和桥联金属离子。这些聚合物表现出一维双链、(4，4)拓扑的2-D层、2-D双层、(6，3)拓扑的2-D层和一维分子阶梯等多种配位结构。结果表明，由于3-BPT具有多种形式的构型和结合方式，R-间苯二甲酸酯的构筑块对设计此类配位阵列具有深刻的取代基效应。然而，金属离子的选择在结构组装中也是重要的，通过非共价相互作用，特别是氢键，低维配位网络进一步扩展到各种三维超分子晶格。我们还研究了它的热稳定性和荧光等固态性质。
A series of nine CoII, CuII, and CdII mixed-ligand coordination complexes with a 3,3′-dipyridyl connector 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole (3-bpt) have been achieved, by changing the incorporated benzenedicarboxylic co-ligands from isophthalic acid (H2ip) to its 5-substituted derivatives 5-nitroisophthalic acid (–NO2, H2nip) and trimesic acid (–COOH, H3tma). All compounds have been structurally determined by the X-ray diffraction technique. It is indicated that most of them are coordination polymers, with the ligands of benzenecarboxylic acids being doubly deprotonated to compensate the charge and bridge the metal ions, except for a monomeric ion-pair product [Co(3-bpt)2(H2O)4]·(H2tma)2·(H2O)2 (1c). These polymers display a variety of coordination frameworks, such as 1-D double-strand chain, 2-D layer with (4,4) topology, 2-D double layer, 2-D layer with (6,3) topology and 1-D molecular ladder etc. The results evidently reveal the profound substituent effect of the R-isophthalate building blocks on engineering such coordination arrays, in virtue of the versatility of 3-bpt with diversiform configurations and binding fashions. Nevertheless, the choice of metal ion is also significant in the structural assembly, and the low-dimensional coordination networks are further extended to diverse 3-D supramolecular crystalline lattices via noncovalent interactions especially hydrogen bonding. Solid-state properties such as thermal stability and fluorescence have also been investigated.