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 that in situ generated catalytic Ag complexes mediate the tecton conversion.

界面超分子自组装代表了构造规则和准晶体材料的有力工具。特别是，复杂的二维分子镶嵌，例如具有规则多边形的半规则阿基米德平铺砖，都具有与其非平凡结构相关的独特属性。但是，它们的形成具有挑战性，因为当前的方法在很大程度上限于前体的直接组装，也就是说，结构形成依赖于分子相互作用而不使用化学转化。在这里，我们选择了乙炔基-碘菲（在几何形状和反应性方面都具有不对称性）作为单个起始前体，以通过原子多平面法在原子平面基板上以长距离顺序生成稀有的半规则（3.4.6.4）阿基米德平铺步骤反应。有趣的是 各个化学转化相会聚，形成对称的炔基-Ag-炔基络合物，成为高产的新技术。通过结合使用显微镜和X射线光谱学工具以及计算模型，我们发现原位生成的催化Ag络合物介导tecton转化。