Division of Supramolecular Chemistry and Medicinal Chemistry, Key Laboratory of Brain Functional Genomics, MOE, and Shanghai Key Laboratory of Brain Functional Genomics, East China Normal University, Shanghai 200062, China.
Dalton Trans. 2010 Oct 7;39(37):8646-51. doi: 10.1039/c000180e. Epub 2010 Aug 11.
The reaction of oxacalix[2]benzene[2]pyrazines and with copper(ii) nitrate, as well as dimeric copper(ii) tetraacetate are presented. Ligands and , both adopt 1,3-alternate conformation, with the two exo-Lewis basic sites spatially oriented outwards. Ligand reacts with copper(ii) ions generated a discrete molecular cage by bridging two ligands via two Cu(2+) ions in the equatorial region. While the reaction of with dicopper(ii) tetraacetate unit resulted in the formation of a discrete supramolecular complex with 1 : 2 stoichiometry between the dicopper(ii) unit and ligand , due to the larger size and axial coordination mode of the dicopper(ii) unit. The conformationally flexible nature of ligand facilitated the formation of coordination polymers and upon interaction with copper(ii) and dicopper(ii) units, respectively. Coordination polymer featured a zigzag structure of alternating ligand and Cu(2+) ion, while in coordination polymer , ligand serves as an axial 2-connected node, propagating the "paddlewheel" dicopper(ii) unit along the polymeric chain.
呈现了氧杂杯[2]芳烃[2]吡嗪与硝酸铜以及二聚醋酸铜的反应。配体和 都采用 1,3-交替构象,两个外路易斯碱性位点向外空间定向。配体通过在赤道区域的两个 Cu(2+) 离子桥接两个配体,与生成的铜(ii)离子反应,形成离散的分子笼。而与二铜(ii)四醋酸盐单元的反应导致形成离散的超分子配合物,二铜(ii)单元与配体之间的化学计量比为 1:2 ,由于二铜(ii)单元的尺寸较大且呈轴向配位模式。配体的构象柔性有利于配位聚合物的形成,并分别与铜(ii)和二铜(ii)单元相互作用。配位聚合物具有交替配体和 Cu(2+) 离子的交错结构,而在配位聚合物中,配体作为轴向 2 连接节点,沿聚合物链传播“桨轮”二铜(ii)单元。