Liu Gao-Feng, Li Zhi-Wei, Huang Zi-Jun, Zhou Zhiyuan, Li Ying-Xian, Huang Anlian, Cai Ziyang, Ouyang Gangfeng, Ye Bao-Hui, Zhang Yue-Biao
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, GBRCE for Functional Molecular Engineering, School of Chemistry, IGCME, Sun Yat-Sen University, Guangzhou 510275, China.
School of Physical Science and Technology, Shanghai Key Laboratory of High-Resolution Electron Microscopy, State Key Laboratory of Advanced Medical Materials and Devices, ShanghaiTech University, Shanghai 201210, China.
J Am Chem Soc. 2025 Jan 15;147(2):1840-1850. doi: 10.1021/jacs.4c13982. Epub 2025 Jan 3.
Covalent organic frameworks (COFs) hold promise in heterogeneous metal catalysis benefiting from their robust, crystalline, and porous structures. However, synthetic challenges persist in prolonged crystallization times, limited metal loading, and uncertain coordination environments. Here, we present the rapid crystallization and versatile metalation of new acetylhydrazone-linked COFs (AH-COFs) by condensation of ketone and hydrazide components, featuring full conversion within 30 min under open-air and mild conditions. The obtained AH-COFs exhibit exceptional thermal and chemical stability, maintaining high crystallinity and microporosity even under harsh conditions. This method shows the versatility of metalation through subcomponent assembly with a wide range of metal centers, and the delicate control of coordination geometry through isoreticular functionalization for fine-tuning of the pore environments and metal catalytic activity. The metalated AH-COFs demonstrate excellent catalytic performance: AH-COF-2-Zn achieves high efficiency in CO cycloaddition, while AH-COF-1-Cu-PSM achieves near-quantitative conversion in copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions, with both catalysts retaining their activity over multiple cycles. This study offers an efficient and versatile method for the rapid crystallization of designable, stable, and functional COFs, heading to practical applications prioritized on efficiency, scalability, and sustainability.
共价有机框架材料（COFs）因其坚固、结晶且多孔的结构，在多相金属催化领域具有广阔前景。然而，合成过程中仍面临诸多挑战，如结晶时间长、金属负载量有限以及配位环境不确定等问题。在此，我们通过酮和酰肼组分的缩合反应，实现了新型乙酰腙连接的COFs（AH-COFs）的快速结晶和多功能金属化，其特点是在露天温和条件下30分钟内即可实现完全转化。所制备的AH-COFs表现出卓越的热稳定性和化学稳定性，即使在苛刻条件下也能保持高结晶度和微孔性。该方法展示了通过与多种金属中心进行亚组分组装实现金属化的多功能性，以及通过等规功能化对配位几何结构进行精细控制，从而微调孔环境和金属催化活性。金属化的AH-COFs表现出优异的催化性能：AH-COF-2-Zn在CO环加成反应中具有高效性，而AH-COF-1-Cu-PSM在铜催化的叠氮-炔环加成（CuAAC）反应中实现了近定量转化，两种催化剂在多个循环中均保持其活性。本研究为可设计、稳定且功能性的COFs的快速结晶提供了一种高效且通用的方法，朝着以效率、可扩展性和可持续性为优先的实际应用迈进。
