Supramolecular cages/vesicles in biology display sophisticated structures and functions by utilizing a few types of protein subunit quasi‐equivalently at distinct geometrical locations. However, synthetic supramolecular cages still lack comparable complexity to reach the high levels of functionality found in natural systems. Herein we report the self‐assembly of giant pentagonal supramolecular prisms (molecular weight >50 kDa) with tetratopic pyridinyl subunits serving different geometrical roles within the structures, and their packing into a novel superstructure with unexpected three‐fold rotational symmetry in a single two‐dimensional layer of crystalline state. The formation of these complicated structures is controlled by both the predetermined angles of the ligands and the mismatched structural tensions created from the multi‐layered geometry of the building blocks. Such a self‐assembly strategy is extensively used by viruses to increase the volume and complexity of capsids and would provide a new approach to construct highly sophisticated supramolecular architectures.

中文翻译：

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双层超分子棱镜由几何上不等价的四位亚基自组装而成。

生物学中的超分子笼子/囊泡通过在不同的几何位置准等价地利用几种类型的蛋白质亚基显示出复杂的结构和功能。然而，合成的超分子笼仍然缺乏可比的复杂性以达到天然系统中高水平的功能。本文中，我们报告了具有五位吡啶基亚基的五角形超分子三棱柱（分子量> 50 kDa）的自组装，这些亚基在结构中起着不同的几何作用，并将它们堆积成一个新的上层结构，并在一个单独的两个结构中具有出乎意料的三重旋转对称性维层为结晶态。这些复杂结构的形成既受配体的预定角度控制，又受积木多层几何结构产生的不匹配结构张力的控制。这种自组装策略已被病毒广泛使用，以增加衣壳的数量和复杂性，并将为构建高度复杂的超分子体系结构提供一种新方法。