Assembly of Zn/Cd coordination polymers containing helixes or polycatenane structures tuned by the tri-pyridyl–bis-amide ligands with different spacer: syntheses, structures, photoluminescent and photocatalytic properties
作者:Xiuli Wang、Jingjing Huang、Lianli Liu、Guocheng Liu、Hongyan Lin、Juwen Zhang、Naili Chen、Yun Qu
DOI:10.1039/c2ce26892b
日期:——
Four new d10 metalâorganic coordination polymers tuned by the âVâ-shaped tri-pyridylâbis-amide ligands with different spacers, namely, [Zn(L1)(BDC)]·H2O (1), [Cd(L1)(BDC)]·H2O (2), [Zn(L2)(BDC)] (3) and [Cd(L2)(BDC)] (4) (L1 = N,Nâ²-bis(pyridine-3-yl)pyridine-2,6-dicarboxamide, L2 = N,Nâ²-bis(pyridine-3-yl)pyridine-3,5-dicarboxamide, H2BDC = 1,4-benzenedicarboxylic acid) have been synthesized under hydrothermal conditions. In complexes 1 and 2, the metal ions are linked by L1 to form left- and right-helical Zn/CdâL1 chains, which are further extended into two-dimensional (2D) wave-like layers by BDC anions. In 3, two L2 ligands link two ZnII ions forming the Zn2(L2)2 loops, which are connected by BDC anions to form a (2·65) topological 2D network. In addition, the large Zn2(L2)2 loops are threaded by the BDC rods from above and below 2D layers so as to form 2D â 3D polyrotaxane and polycatenane structures. In 4, the CdII ions are linked by L2 ligands to generate 1D double chain ribbons with Cd2(L2)2 loops, which are further connected by the BDC linkers to form a 3D framework. Two identical 3D frameworks interpenetrate each other in a twofold mode, giving rise to a polyrotaxane and polycatenane array, which is relative limited. The diverse structures of complexes 1â4 demonstrate that the tri-pyridylâbis-amide ligands and the central metals have significant effect on the final structures. The thermal stability and fluorescent properties of complexes 1â4 have been investigated. In addition, the title complexes exhibit photocatalytic activity for dye methylene blue degradation under UV light.
四种新型 d10 金属有机配位聚合物由带有不同间隔物的 "V "型三吡啶基双酰胺配体调谐而成,即 [Zn(L1)(BDC)]Â-H2O (1)、[Cd(L1)(BDC)]Â-H2O (2)、[Zn(L2)(BDC)](3) 和 [Cd(L2)(BDC)] (4) (L1 = N,N²-双(吡啶-3-基))、在水热条件下合成了 [Zn(L2)(BDC)] (3) 和 [Cd(L2)(BDC)] (4)(L1 = N,Nâ²-双(吡啶-3-基)吡啶-2,6-二甲酰胺,L2 = N,Nâ²-双(吡啶-3-基)吡啶-3,5-二甲酰胺,H2BDC = 1,4-苯二甲酸)。在复合物 1 和 2 中,金属离子通过 L1 连接形成左螺旋和右螺旋 Zn/CdâL1 链,BDC 阴离子进一步将其扩展成二维(2D)波状层。在 3 中,两个 L2 配体连接两个 ZnII 离子,形成 Zn2(L2)2 环,这些环由 BDC 阴离子连接,形成一个 (2Â-65) 拓扑二维网络。此外,Zn2(L2)2 大环被二维层上下的 BDC 杆穿入,从而形成二维-三维聚罗他烷和聚卡他烯烷结构。在 4 中,CdII 离子通过 L2 配体连接,生成带有 Cd2(L2)2 环的一维双链带,这些双链带通过 BDC 连接器进一步连接,形成三维框架。两个相同的三维框架以二重模式相互渗透,形成了相对有限的多罗他烷和多卡他烷阵列。复合物 1â4 的不同结构表明,三吡啶基双酰胺配体和中心金属对最终结构具有重要影响。研究还考察了 1â4 复合物的热稳定性和荧光特性。此外,标题配合物在紫外线下具有降解染料亚甲基蓝的光催化活性。