Wang Jin, Yang Shengyi, Zhang Liang, Xiao Xuedong, Deng Zihao, Chen Xinmeng, Liu Cheng, Huang Gongyue, Kwok Ryan T K, Lam Jacky W Y, Tang Ben Zhong
Department of Chemistry and the Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong 999077, P. R. China.
Institute of Zhejiang University─Quzhou, Quzhou, Zhejiang 324000, P. R. China.
J Am Chem Soc. 2024 Nov 13;146(45):31042-31052. doi: 10.1021/jacs.4c10713. Epub 2024 Nov 4.
The unique ionic channels and highly polar pore structures have distinguished crystalline porous organic salts (CPOSs) from conventional porous frameworks in the past decade. Up to now, CPOSs were all constructed by a monoionic strategy, in which two types of building units individually bearing anionic or cationic groups were introduced, thus increasing complexity in the synthesis of CPOSs. In this study, by utilizing stereoisomeric compounds of TPE-NS-Z or TPE-NS-E bearing both anionic and cationic groups as a single building unit, the zwitterionic strategy was proven feasible in constructing CPOSs. Benefiting from the single building unit, the zwitterionic strategy simplified the preparation process and reduced the difficulty in studying the aggregation behavior of building units into CPOSs. And also, this novel strategy enabled precise control of the finally obtained CPOSs through fine-tuning of the initial building units. Surprisingly, the special parallel/vertical alternated stacking mode and unique ionic interaction networks in the crystal structure provided the flexible pore characteristic of CPOS-E, which further guaranteed the multitime controllable release of highly polar chemicals in different solvents.
在过去十年中，独特的离子通道和高度极性的孔结构使结晶多孔有机盐（CPOSs）有别于传统的多孔骨架。到目前为止，CPOSs都是通过单离子策略构建的，即引入分别带有阴离子或阳离子基团的两种类型的构建单元，从而增加了CPOSs合成的复杂性。在本研究中，通过使用同时带有阴离子和阳离子基团的TPE-NS-Z或TPE-NS-E的立体异构体化合物作为单一构建单元，证明了两性离子策略在构建CPOSs方面是可行的。得益于单一构建单元，两性离子策略简化了制备过程，并降低了研究构建单元聚集成CPOSs的聚集行为的难度。此外，这种新策略能够通过对初始构建单元的微调来精确控制最终得到的CPOSs。令人惊讶的是，晶体结构中特殊的平行/垂直交替堆积模式和独特的离子相互作用网络赋予了CPOS-E灵活的孔特征，这进一步保证了高极性化学物质在不同溶剂中的多次可控释放。
