Wu Huang, Wang Yu, Đorđević Luka, Kundu Pramita, Bhunia Surojit, Chen Aspen X-Y, Feng Liang, Shen Dengke, Liu Wenqi, Zhang Long, Song Bo, Wu Guangcheng, Liu Bai-Tong, Yang Moon Young, Yang Yong, Stern Charlotte L, Stupp Samuel I, Goddard William A, Hu Wenping, Stoddart J Fraser
Key Laboratory of Organic Integrated Circuit, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, Tianjin University, Tianjin, China.
Department of Chemistry, The University of Hong Kong, Hong Kong SAR, China.
Nature. 2025 Jan;637(8045):347-353. doi: 10.1038/s41586-024-08266-3. Epub 2025 Jan 8.
Mimicking the superstructures and properties of spherical biological encapsulants such as viral capsids and ferritin offers viable pathways to understand their chiral assemblies and functional roles in living systems. However, stereospecific assembly of artificial polyhedra with mechanical properties and guest-binding attributes akin to biological encapsulants remains a formidable challenge. Here we report the stereospecific assembly of dynamic supramolecular snub cubes from 12 helical macrocycles, which are held together by 144 weak C-H hydrogen bonds. The enantiomerically pure snub cubes, which have external diameters of 5.1 nm, contain 2,712 atoms and chiral cavities with volumes of 6,215 Å. The stereospecific assembly of left- and right-handed snub cubes was achieved by means of a hierarchical chirality transfer protocol, which was streamlined by diastereoselective crystallization. In addition to their reversible photochromic behaviour, the snub cubes exhibit photocontrollable elasticity and hardness in their crystalline states. The snub cubes can accommodate numerous small guest molecules simultaneously and encapsulate two different guest molecules separately inside the uniquely distinct compartments in their frameworks. This research expands the scope of artificial supramolecular assemblies to imitate the chiral superstructures, dynamic features and binding properties of spherical biomacromolecules and also establishes a protocol for construction of crystalline materials with photocontrollable mechanical properties.
模仿病毒衣壳和铁蛋白等球形生物包膜的超结构和性质，为理解它们在生命系统中的手性组装和功能作用提供了可行的途径。然而，具有类似于生物包膜的机械性能和客体结合属性的人工多面体的立体定向组装仍然是一项艰巨的挑战。在此，我们报告了由12个螺旋大环通过144个弱C-H氢键结合在一起形成的动态超分子截顶立方体的立体定向组装。对映体纯的截顶立方体的外径为5.1纳米，包含2712个原子，其手性空腔的体积为6215埃。左旋和右旋截顶立方体的立体定向组装是通过分级手性转移协议实现的，该协议通过非对映选择性结晶得到了简化。除了具有可逆的光致变色行为外，截顶立方体在其结晶状态下还表现出光控弹性和硬度。截顶立方体可以同时容纳许多小分子客体，并将两种不同的客体分子分别封装在其框架中独特的不同隔室内。这项研究扩展了人工超分子组装的范围，以模仿球形生物大分子的手性超结构、动态特征和结合特性，同时也建立了一种构建具有光控机械性能的晶体材料的方法。
