Beijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry and Chemical Industry, College of Environmental and Energy Engineering, Beijing University of Technology , Beijing 100124, P. R. China.
J Am Chem Soc. 2014 Aug 6;136(31):10921-9. doi: 10.1021/ja502295c. Epub 2014 Jul 25.
Metal-metal bonding interactions have been used to generate a number of unique supramolecular assemblies with fascinating functions. We presented here a new class of gold(I)-containing metallosupramolecular cages and cage-built two-dimensional (2-D) arrays of {Au8L2}n (n = 1 or ∞, L = tetrakis-dithiocarbamato-calix[4]arene, TDCC), 1-3, which are constructed from the self-assembly of deep-cavitand calix[4]arene-based supramolecular cages consisting of octanuclear Au(I) motifs. Synchrotron radiation X-ray diffraction structural analyses of 1-3 revealed their quadruple-stranded helicate dimeric cage structure and the presence of 2-D arrays of cages linked together by inter- and intramolecular Au(I)···Au(I) interactions. Electronic absorption and emission studies of complexes 1-3 indicated the occurrence of a programmable self-assembly process in a concentration-dependent stepwise manner with the links built via aurophilic interactions. These novel gold(I) supramolecular cages exhibited green phosphorescence and have been shown to serve as highly selective proof-of-concept luminescent sensors toward Ag(I) cation among various competitive transition-metal ions.
金属-金属键相互作用已被用于生成许多具有迷人功能的独特超分子组装体。我们在这里展示了一类新型的含金（I）的金属超分子笼和笼构建的二维（2-D）{Au8L2}n（n=1 或 ∞，L=四硫代碳酰二氨合杯[4]芳烃，TDCC）的阵列，1-3，它们是由包含八核 Au（I）基元的深穴杯[4]芳烃基超分子笼的自组装构建而成。1-3 的同步辐射 X 射线衍射结构分析揭示了它们的四重螺旋二聚体笼状结构以及通过分子内和分子间的 Au（I）···Au（I）相互作用连接在一起的笼状 2-D 阵列的存在。配合物 1-3 的电子吸收和发射研究表明，存在可编程的自组装过程，该过程以浓度依赖的分步方式进行，通过金键合相互作用构建键。这些新型的金（I）超分子笼表现出绿色磷光，并已被证明是对各种竞争过渡金属离子中 Ag（I）阳离子具有高度选择性的概念验证发光传感器。
