Hussain Navid, Bhardwaj Vimal K
Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab 140001, India.
Dalton Trans. 2016 May 4;45(18):7697-707. doi: 10.1039/c6dt00612d.
Three new Cu(ii) coordination polymers, namely, {[Cu3(L(1))(NO3)2(DMF)(H2O)]·3(DMF)}n (), [Cu3(L(1))(Cl)2(DMF)2]n () and [Cu3(L(2))(NO3)4(H2O)4]n (), were synthesized from pyridine-2,6-dicarbohydrazide based imine linked tritopic ligands. All the complexes were characterized using elemental analysis, IR, UV-vis spectroscopy and ESI-MS. The solid state structures of complexes were determined using single crystal X-ray crystallography. The complexes contain trinuclear copper units connected through different anions that lead to the formation of one dimensional (ID) chain structures. Depending upon the anion of the copper salt and donor atoms of the ligands used in complexation, a small variation in the structures was observed. In complex , the trinuclear copper units are connected by phenoxo-bridging (μ2-O(-)) along with one coordinated water molecule, whereas complex is connected through chloride bridging (μ2-Cl) and complex is connected through nitrate ions (μ-[O-N-O]) along with four water molecules. Photo-catalytic activities of the synthesized complexes () were investigated. All the complexes were found to be photo-catalytically active; however, the distinct coordination environment of the metal ions (i.e. difference in the coordinated water molecules and donor sites of ligands) played a significant role in the catalytic activities. Therefore, this study presents comparative photo-catalytic studies of different coordination environments of metal ions in one-dimensional Cu(ii) coordination polymers. The results provide a potential pathway for the rational design of more efficient photo-catalysts.
通过基于吡啶 - 2,6 - 二碳酰肼的亚胺连接三齿配体合成了三种新型铜（II）配位聚合物，即{[Cu3(L(1))(NO3)2(DMF)(H2O)]·3(DMF)}n（）、[Cu3(L(1))(Cl)2(DMF)2]n（）和[Cu3(L(2))(NO3)4(H2O)4]n（）。所有配合物均通过元素分析、红外光谱、紫外 - 可见光谱和电喷雾电离质谱进行表征。配合物的固态结构通过单晶X射线晶体学确定。这些配合物包含通过不同阴离子连接的三核铜单元，导致形成一维（ID）链结构。根据配合物中所用铜盐的阴离子和配体的供体原子，观察到结构上有微小变化。在配合物中，三核铜单元通过苯氧桥连（μ2 - O(-)）以及一个配位水分子相连，而配合物通过氯桥连（μ2 - Cl）相连，配合物通过硝酸根离子（μ - [O - N - O]）以及四个水分子相连。对合成的配合物（）的光催化活性进行了研究。发现所有配合物均具有光催化活性；然而，金属离子独特的配位环境（即配位水分子和配体供体位点的差异）在催化活性中起了重要作用。因此，本研究展示了一维铜（II）配位聚合物中金属离子不同配位环境的比较光催化研究。结果为合理设计更高效的光催化剂提供了一条潜在途径。
