Complex supramolecular interfacial tessellation through convergent multi-step reaction of a dissymmetric simple organic precursor.
Complex supramolecular interfacial tessellation through convergent multi-step reaction of a dissymmetric simple organic precursor.
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DOI：
10.1038/nchem.2924
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发表时间：
2018-01
期刊：
影响因子：
21.8
通讯作者：
Yi‐Qi Zhang;M. Paszkiewicz;P. Du;Liding Zhang;Tao Lin;Zhi Chen;S. Klyatskaya;M. Ruben;A. Seitsonen;J. Barth;F. Klappenberger
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文献类型：
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作者：
Yi‐Qi Zhang;M. Paszkiewicz;P. Du;Liding Zhang;Tao Lin;Zhi Chen;S. Klyatskaya;M. Ruben;A. Seitsonen;J. Barth;F. Klappenberger
界面超分子自组装是构筑规则和准晶材料的有力工具。特别是，复杂的二维分子镶嵌，如半正则阿基米德镶嵌与正多边形，承诺独特的性质，其非平凡的结构。然而，它们的形成是具有挑战性的，因为目前的方法在很大程度上限于前体的直接组装，即结构形成依赖于分子相互作用而不使用化学转化。在这里，我们选择乙炔基碘菲（其特征在于在几何形状和反应性的不对称性）作为单一的起始前体，通过多步反应在原子级平坦的基底上产生具有长程有序的罕见的半规则（3.4.6.4）阿基米德镶嵌。有趣的是，个别的化学转化收敛，形成一个对称的炔基-银-炔基复合物作为新的tecton在高产率。使用显微镜和X-射线光谱工具的组合，以及计算建模，我们表明thatin原位生成的催化银配合物介导的构造转换。
Interfacial supramolecular self-assembly represents a powerful tool for constructing regular and quasicrystalline materials. In particular, complex two-dimensional molecular tessellations, such as semi-regular Archimedean tilings with regular polygons, promise unique properties related to their nontrivial structures. However, their formation is challenging, because current methods are largely limited to the direct assembly of precursors, that is, where structure formation relies on molecular interactions without using chemical transformations. Here, we have chosen ethynyl-iodophenanthrene (which features dissymmetry in both geometry and reactivity) as a single starting precursor to generate the rare semi-regular (3.4.6.4) Archimedean tiling with long-range order on an atomically flat substrate through a multi-step reaction. Intriguingly, the individual chemical transformations converge to form a symmetric alkynyl–Ag–alkynyl complex as the new tecton in high yields. Using a combination of microscopy and X-ray spectroscopy tools, as well as computational modelling, we show thatin situgenerated catalytic Ag complexes mediate the tecton conversion.