Li Yusen, Chen Qing, Xu Tiantian, Xie Zhen, Liu Jingjuan, Yu Xiang, Ma Shengqian, Qin Tianshi, Chen Long
Department of Chemistry, Institute of Molecular Plus, and Tianjin Key Laboratory of Molecular Optoelectronic Science , Tianjin University , Tianjin 300072 , P. R. China.
Institute of Advanced Materials (IAM) , Nanjing Tech University (Nanjing Tech) , Nanjing 210009 , P. R. China.
J Am Chem Soc. 2019 Sep 4;141(35):13822-13828. doi: 10.1021/jacs.9b03463. Epub 2019 Aug 23.
We herein develop a two-in-one molecular design strategy for facile synthesis of 2D imine based covalent organic frameworks (COFs). The integration of two different functional groups (i.e., formyl and amino groups) in one simple pyrene molecule affords a bifunctional building block: 1,6-bis(4-formylphenyl)-3,8-bis(4-aminophenyl)pyrene (BFBAPy). Highly crystalline and porous Py-COFs can be easily prepared by the self-condensation of BFBAPy in various solvents, such as CHCl, CHCl, tetrahydrofuran, methanol, ethanol, acetonitrile, and dimethylacetamide, etc. The current work, to the best of our knowledge, is a rare case of COF synthesis that exhibits excellent solvent adaptability. Highly crystalline Py-COF thin films have been facilely fabricated on various substrates and exhibit potential applications in hole transporting layers for perovskite solar cells. Furthermore, the versatility of this two-in-one strategy was also verified by two additional examples. The current work dramatically reduces the difficulty of COF synthesis, and such two-in-one strategy is anticipated to be applicable for the synthesis of other COFs constructed by different building blocks and linkages.
我们在此开发了一种二合一的分子设计策略，用于简便合成基于二维亚胺的共价有机框架（COF）。在一个简单的芘分子中整合两个不同的官能团（即甲酰基和氨基），得到一种双功能构建单元：1,6-双（4-甲酰基苯基）-3,8-双（4-氨基苯基）芘（BFBAPy）。通过BFBAPy在各种溶剂（如CHCl、CHCl、四氢呋喃、甲醇、乙醇、乙腈和二甲基乙酰胺等）中的自缩合，可以轻松制备出高度结晶且多孔的Py-COF。据我们所知，目前的工作是COF合成中罕见的一例，展现出优异的溶剂适应性。高度结晶的Py-COF薄膜已在各种基底上轻松制备，并在钙钛矿太阳能电池的空穴传输层中展现出潜在应用。此外，通过另外两个例子也验证了这种二合一策略的通用性。目前的工作极大地降低了COF合成的难度，并且预计这种二合一策略适用于由不同构建单元和连接方式构建的其他COF的合成。
