Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly
Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly
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DOI：
10.1073/pnas.1222713110
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发表时间：
2013-04-23
影响因子：
11.1
通讯作者：
Barth, Johannes V.
中科院分区：
文献类型：
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作者：
Ecija, David;Urgel, Jose I.;Barth, Johannes V.
用正多边形对欧几里得平面进行镶嵌自古以来就被人们所关注，并呈现出包括数学、艺术和晶体学在内的有趣方面。大量的努力致力于在分子水平上设计特定的2D界面镶嵌，但具有不同五顶点图案的周期性图案仍然难以捉摸。在这里，我们报告了一个直接扫描隧道显微镜研究铈的线性聚苯分子连接器与终端腈基团在光滑的Ag（111）贵金属表面的组装。我们证明了自发形成的五倍Ce-配体配位基序，这是平面的和灵活的，使顶点同时连接三角形和正方形多边形可以表示。通过调节稀土金属中心与配体的浓度和化学计量比，可以制备具有十二聚体单元和表面限制的金属-有机配位网络的分级组装体，从而产生半规则的阿基米德斜方形镶嵌。
The tessellation of the Euclidean plane by regular polygons has been contemplated since ancient times and presents intriguing aspects embracing mathematics, art, and crystallography. Significant efforts were devoted to engineer specific 2D interfacial tessellations at the molecular level, but periodic patterns with distinct five-vertex motifs remained elusive. Here, we report a direct scanning tunneling microscopy investigation on the cerium-directed assembly of linear polyphenyl molecular linkers with terminal carbonitrile groups on a smooth Ag(111) noble-metal surface. We demonstrate the spontaneous formation of fivefold Ce-ligand coordination motifs, which are planar and flexible, such that vertices connecting simultaneously trigonal and square polygons can be expressed. By tuning the concentration and the stoichiometric ratio of rare-earth metal centers to ligands, a hierarchic assembly with dodecameric units and a surface-confined metal-organic coordination network yielding the semiregular Archimedean snub square tiling could be fabricated.