Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Environmental Research at Great Bay, Guangzhou University, Guangzhou, China.
Department of Chemistry, University of South Florida, Tampa, FL, USA.
Nat Chem. 2020 May;12(5):468-474. doi: 10.1038/s41557-020-0454-z. Epub 2020 Apr 13.
For the past three decades, the coordination-driven self-assembly of three-dimensional structures has undergone rapid progress; however, parallel efforts to create large discrete two-dimensional architectures-as opposed to polymers-have met with limited success. The synthesis of metallo-supramolecular systems with well-defined shapes and sizes in the range of 10-100 nm remains challenging. Here we report the construction of a series of giant supramolecular hexagonal grids, with diameters on the order of 20 nm and molecular weights greater than 65 kDa, through a combination of intra- and intermolecular metal-mediated self-assembly steps. The hexagonal intermediates and the resulting self-assembled grid architectures were imaged at submolecular resolution by scanning tunnelling microscopy. Characterization (including by scanning tunnelling spectroscopy) enabled the unambiguous atomic-scale determination of fourteen hexagonal grid isomers.
在过去的三十年中，基于协调驱动的三维结构自组装取得了快速进展；然而，与之相反的是，人们在构建离散的二维结构方面的努力却收效甚微，仅限于聚合物。在 10-100nm 的范围内，合成具有明确形状和尺寸的金属超分子体系仍然具有挑战性。在这里，我们报告了一系列巨型超分子六方网格的构建，其直径约为 20nm，分子量大于 65kDa，这是通过分子内和分子间金属介导的自组装步骤相结合实现的。通过扫描隧道显微镜，在亚分子分辨率下对六方中间体和所得的自组装网格结构进行了成像。通过（包括扫描隧道光谱法）的表征，能够在原子尺度上明确确定十四个六方网格异构体。
