Sustainable Technology Research Center, Shanghai Advanced Research Institute, Chinese Academy of Science, Shanghai 201210, China.
Inorg Chem. 2013 Aug 19;52(16):9309-19. doi: 10.1021/ic400751n. Epub 2013 Aug 8.
A novel trispyrazine-pillared prismatic bicycooxacalixaromatic ligand L is synthesized, and its application in metal-mediated self-assembly is described. Under self-assembly conditions, single chain, double-stranded cross-linked coordination polymer and two-dimensional (2D) coordination polymeric networks were formed via M-L (Ag(+), Cu(2+), and Zn(2+)) coordinative interactions. Structural analyses revealed that the antiparallelly arranged one-dimensional coordination polymers (Cu(2+) and Zn(2+)) are arranged to generate well-defined voids to host aromatic guests (benzene) via C-H···π and π···π interactions, while the double-stranded cross-linked coordination polymer (Ag(+)) contains a rhomboidal [Ag2(L(3))2] (L(3): tridentate ligand) cage motif to include a benzene guest; the "thicker" (thickness: ac 5 Å) 2D coordination polymeric networks (Ag(+), Cu(2+), and Zn(2+)), however, are all formed by connection of one or two kinds of topologically different metallomacrocyclic cage units. These unique metallomacrocyclic cage units in the 2D coordination polymeric networks are capable of hosting different guest species. For instance, the rhomboidal [M2(L(3))2] (M = Ag(+), Cu(2+)) cage units were found to host a benzene or a nitrate anion; a hexahedral [M3(L(3))3] (M = Ag(+)) cage was found to host a ligand L or a DMF molecule; the hexahedral [M4(L(3))4] (M = Cu(2+)) cage was found to host four solvent molecules of benzene; and the rectangular [M3(L(3))3] (M = Cu(2+), Zn(2+)) cage units, however, were found to host two THF molecules. The results highlight the potential of ligand L for applications in the construction of "thicker" 2D coordination polymeric networks with well-defined metallomacrocyclic cage units capable of hosting various guest species.
一种新型三嗪基撑柱式双环氧杂杯芳烃配体 L 被合成，并描述了其在金属介导的自组装中的应用。在自组装条件下，通过 M-L（Ag(+)、Cu(2+)和 Zn(2+)）配位相互作用，形成了单链、双链交联配位聚合物和二维（2D）配位聚合物网络。结构分析表明，反平行排列的一维配位聚合物（Cu(2+)和 Zn(2+)）通过 C-H···π 和 π···π 相互作用排列，以生成明确的空穴来容纳苯等芳烃客体，而双链交联配位聚合物（Ag(+)）则包含一个菱形的[Ag2(L(3))2]（L(3)：三齿配体）笼状结构来包含苯客体；“更厚”（厚度：ac 5 Å）的 2D 配位聚合物网络（Ag(+)、Cu(2+)和 Zn(2+)）则是由一个或两个拓扑不同的金属大环笼单元的连接形成的。这些独特的金属大环笼单元在 2D 配位聚合物网络中能够容纳不同的客体物种。例如，菱形的[M2(L(3))2]（M = Ag(+)、Cu(2+)）笼单元被发现可以容纳苯或硝酸根阴离子；六方的[M3(L(3))3]（M = Ag(+)）笼单元被发现可以容纳一个配体 L 或 DMF 分子；六方的[M4(L(3))4]（M = Cu(2+)）笼单元被发现可以容纳四个苯溶剂分子；而矩形的[M3(L(3))3]（M = Cu(2+)、Zn(2+)）笼单元则被发现可以容纳两个 THF 分子。这些结果突出了配体 L 在构建具有明确金属大环笼单元的“更厚”2D 配位聚合物网络方面的潜力，这些金属大环笼单元可以容纳各种客体物种。
