Crystalline solids with structural motifs of five-vertex semi-regular Archimedean tessellations are referred to as quasicrystal approximants (ACs). However, the synthesis of crystalline porous frameworks with AC patterns remains a challenge because of a limited number of planar 5-fold nodes. Geometrically, Cairo pentagonal tiling, the dual form of the snub square tiling, enriches the access of ACs. We serendipitously obtain a two-dimensional metal-organic framework (MOF) with Cairo pentagonal tiling by combining the square-planar and triangular nodes. Reticular chemistry further allows the synthesis of an isoreticular MOF with planar tessellation of pentagons. Such isoreticular design is rarely presented in reported AC structures. Our study not only enriches the structural database of ACs but also paves the way for AC-MOFs with programmable structures and functionalities.

具有五顶点半正则阿基米德镶嵌结构图案的晶体固体被称为准晶体近似体（AC）。然而，由于平面五折节点数量有限，具有 AC 图案的结晶多孔框架的合成仍然是一个挑战。从几何角度来看，开罗五边形瓷砖（短方形瓷砖的双重形式）丰富了空调的通道。通过结合方形平面和三角形节点，我们偶然获得了具有开罗五边形平铺的二维金属有机框架（MOF）。网状化学进一步允许合成具有五边形平面镶嵌的等网状 MOF。这种等网状设计很少出现在已报道的 AC 结构中。我们的研究不仅丰富了AC的结构数据库，而且为具有可编程结构和功能的AC-MOF铺平了道路。