Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science , Northwest University , Xi'an 710069 , P. R. China.
Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics , Chinese Academy of Sciences , Shanghai 201204 , P. R. China.
J Am Chem Soc. 2018 Jun 6;140(22):7005-7011. doi: 10.1021/jacs.8b03856. Epub 2018 May 22.
Recently, porous framework materials with various network-type structures have been constructed via several different approaches, such as coordination interactions, reversible covalent bonds, and non-covalent interactions. Here, we have combined the concepts of supramolecular coordination complex (SCC) and metal-organic framework to offer a new strategy to construct a diamondoid supramolecular coordination framework (SCF) from an adamantanoid supramolecular coordination cage as the tetrahedral node and a difunctional Pt(II) ligand as the linear linker via stepwise orientation-induced supramolecular coordination. The adamantanoid supramolecular coordination cage has four uncoordinated pyridyl groups, which serve as the four vertexes of the tetrahedral geometry in the diamondoid framework. As a result, this diamondoid SCF exhibits an adamantanoid-to-adamantanoid substructure with two sets of pores, including the interior cavity of the adamantanoid cage and the extended adamantanoid space between the individual cages in the framework. In addition, the shape-controllable and highly ordered self-assembly of nanometer-sized diamondoid SCF is observed as micrometer-sized regular octahedrons by evaporation under heating in DMSO. This study demonstrates the potential application of supramolecular coordination complexes in the precise construction of highly regulated porous framework materials.
最近，通过多种不同的方法，如配位相互作用、可逆共价键和非共价相互作用，构建了具有各种网络型结构的多孔骨架材料。在这里，我们结合超分子配位配合物（SCC）和金属有机骨架的概念，提供了一种新的策略，通过逐步取向诱导的超分子配位，从金刚烷型超分子配位笼作为四面体节点和双功能 Pt(II)配体作为线性连接体构建金刚烷型超分子配位骨架（SCF）。金刚烷型超分子配位笼具有四个未配位的吡啶基，作为金刚石骨架中四面体几何形状的四个顶点。因此，这种金刚石型 SCF 表现出具有两组孔的金刚烷型-金刚烷型亚结构，包括金刚烷笼的内腔和骨架中各个笼之间的扩展金刚烷空间。此外，通过在 DMSO 中加热蒸发，观察到纳米级金刚石型 SCF 的形状可控和高度有序的自组装，形成微米级的规则八面体。这项研究证明了超分子配位配合物在精确构建高度调控多孔骨架材料方面的潜在应用。
