Yang Zhenyu, Yu Chunyang, Ding Junjie, Chen Lihua, Liu Huiyu, Ye Yangzhi, Li Pan, Chen Jiaolong, Wu Kim Jiayi, Zhu Qiang-Yu, Zhao Yu-Quan, Liu Xiaoning, Zhuang Xiaodong, Zhang Shaodong
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, 800 Dongchuan Road, 200240, Shanghai, China.
School of Physical Science and Technology, ShanghaiTech University, 393 Huaxia Middle Road, 200120, Shanghai, China.
Nat Commun. 2021 Oct 21;12(1):6124. doi: 10.1038/s41467-021-26397-3.
A variety of organic cages with different geometries have been developed during the last decade, most of them exhibiting a single cavity. In contrast, the number of organic cages featuring a pair of cavities remains scarce. These structures may pave the way towards novel porous materials with emergent properties and functions.We herein report on rational design of a three-dimensional hexaformyl precursor 1, which exhibits two types of conformers, i.e. Conformer-1 and -2, with different cleft positions and sizes. Aided by molecular dynamics simulations, we select two triamino conformation capturers (denoted CC). Small-sized CC-1 selectively capture Conformer-1 by matching its cleft size, while the large-sized CC-2 is able to match and capture both conformers. This strategy allows the formation of three compounds with twin cavities, which we coin diphane. The self-assembly of diphane units results in superstructures with tunable proton conductivity, which reaches up to 1.37×10 S cm.
在过去十年中，人们开发了各种具有不同几何形状的有机笼，其中大多数都有一个单一的空腔。相比之下，具有一对空腔的有机笼数量仍然稀少。这些结构可能为具有新特性和功能的新型多孔材料铺平道路。我们在此报告一种三维六甲酰基前体1的合理设计，它表现出两种类型的构象异构体，即构象异构体-1和-2，具有不同的裂缝位置和尺寸。在分子动力学模拟的帮助下，我们选择了两种三氨基构象捕获剂（表示为CC）。小尺寸的CC-1通过匹配其裂缝大小选择性地捕获构象异构体-1，而大尺寸的CC-2能够匹配并捕获两种构象异构体。这种策略允许形成三种具有双空腔的化合物，我们将其命名为双环笼。双环笼单元的自组装产生了具有可调质子传导率的超结构，其高达1.37×10 S cm。 （注：原文中“1.37×10 S cm”这里的表述似乎有误，推测可能是“1.37×10 -3 S cm”之类的正确形式）
