Li Xing, Qiao Jingsi, Chee See Wee, Xu Hai-Sen, Zhao Xiaoxu, Choi Hwa Seob, Yu Wei, Quek Su Ying, Mirsaidov Utkur, Loh Kian Ping
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.
Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, 6 Science Drive 2, Singapore 117546, Singapore.
J Am Chem Soc. 2020 Mar 11;142(10):4932-4943. doi: 10.1021/jacs.0c00553. Epub 2020 Mar 2.
Covalent organic frameworks are an emerging class of porous crystalline organic materials that can be designed and synthesized from the bottom up. Despite progress made in synthesizing COFs of diverse topologies, the synthesis methods are often tedious and unscalable, hampering practical applications. Herein, we demonstrate a scalable, robust method of producing highly crystalline acylhydrazone two-dimensional (2D) COFs with diversified structures (six examples) under open and stirred conditions, with growth typically completed in only 30 min. Our strategy involves selecting molecular building blocks that have bond dipole moments with spatial orientations that favor antiparallel stacking and whose structure allows the restriction of intramolecular bond rotation (RIR) via intra- and interlayer hydrogen bonding. This method is widely applicable for hydrazide linkers containing various side-chain functionalities and topicities. By this strategy, the gram-scale synthesis of two highly crystalline COFs (up to 1.4 g yield) was obtained in a one-pot reaction within 30 min.
共价有机框架是一类新兴的多孔晶体有机材料，可以自下而上地进行设计和合成。尽管在合成各种拓扑结构的共价有机框架方面取得了进展，但合成方法往往繁琐且无法规模化，阻碍了实际应用。在此，我们展示了一种可扩展、稳健的方法，可在开放搅拌条件下制备具有多样化结构（六个实例）的高度结晶的酰腙二维（2D）共价有机框架，生长通常仅需30分钟即可完成。我们的策略包括选择具有键偶极矩且空间取向有利于反平行堆积的分子构建块，其结构允许通过层内和层间氢键限制分子内键旋转（RIR）。该方法广泛适用于含有各种侧链官能团和拓扑结构的酰肼连接体。通过这种策略，在30分钟内通过一锅反应获得了两种高度结晶的共价有机框架的克级合成产物（产率高达1.4克）。
