He Yan-Ping, Chen Guang-Hui, Li De-Jing, Li Qiao-Hong, Zhang Lei, Zhang Jian
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Angew Chem Int Ed Engl. 2021 Feb 8;60(6):2920-2923. doi: 10.1002/anie.202013977. Epub 2020 Dec 10.
Many metal-organic cages (MOCs) and a few hydrogen-bonded organic cages (HOCs) have been investigated, but little is reported about cooperative self-assembly of MOCs and HOCs. Herein, we describe an unprecedented MOC&HOC co-crystal composed of tetrahedral Ti L (L=embonate) cages and in-situ-generated [(NH ) (TIPA) ] (TIPA=tris(4-(1H-1,2,4-triazol-1-yl)phenyl)amine) cages. Chiral transfer is observed from the enantiopure Ti L cage to enantiopure [(NH ) (TIPA) ] cage. Two homochiral supramolecular frameworks with opposite handedness (PTC-235(Δ) and PTC-235(Λ)) are formed. Such MOC&HOC co-crystal features high stability in water and other solvents, affording single-crystal-to-single-crystal transformation to trap CH CN molecules and identify disordered NH cations. A tablet pressing method is developed to test the third-order nonlinear optical property of KBr-based PTC-235 thin film. Such a thin film exhibits an excellent optical limiting effect.
许多金属有机笼（MOCs）和少数氢键有机笼（HOCs）已被研究，但关于MOCs和HOCs的协同自组装报道较少。在此，我们描述了一种由四面体Ti L（L = 恩波酸盐）笼和原位生成的[(NH ) (TIPA) ]（TIPA = 三（4 -（1H - 1,2,4 - 三唑 - 1 - 基）苯基）胺）笼组成的前所未有的MOC&HOC共晶体。观察到从对映纯的Ti L笼到手性纯的[(NH ) (TIPA) ]笼的手性转移。形成了两种具有相反手性的同手性超分子框架（PTC - 235(Δ)和PTC - 235(Λ)）。这种MOC&HOC共晶体在水和其他溶剂中具有高稳定性，实现单晶到单晶的转变以捕获CH CN分子并识别无序的NH 阳离子。开发了一种压片方法来测试基于KBr的PTC - 235薄膜的三阶非线性光学性质。这种薄膜表现出优异的光限幅效应。
