Chen Qing, Lin Mengdi, Li Xia, Du Zhenglin, Liu Yandie, Tang Yisong, Yan Yong, Zhu Kelong
School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
School of Chemistry, South China Normal University, Guangzhou, 510006, China.
Angew Chem Int Ed Engl. 2024 Sep 9;63(37):e202407575. doi: 10.1002/anie.202407575. Epub 2024 Aug 6.
Crown ethers (CEs), known for their exceptional host-guest complexation, offer potential as linkers in covalent organic frameworks (COFs) for enhanced performance in catalysis and host-guest binding. However, their highly flexible conformation and low symmetry limit the diversity of CE-derived COFs. Here, we introduce a novel C-symmetrical azacrown ether (ACE) building block, tris(pyrido)[18]crown-6 (TPy18C6), for COF fabrication (ACE-COF-1 and ACE-COF-2) via reticular synthesis. This approach enables precise integration of CEs into COFs, enhancing Ni ion immobilization while maintaining crystallinity. The resulting Ni-doped COFs (Ni@ACE-COF-1 and Ni@ACE-COF-2) exhibit high discharge capacity (up to 1.27 mAh ⋅ cm at 8 mA ⋅ cm) and exceptional cycling stability (>1000 cycles) as cathode materials in aqueous alkaline nickel-zinc batteries. This study serves as an exemplar of the seamless integration of macrocyclic chemistry and reticular chemistry, laying the groundwork for extending the macrocyclic-synthon driven strategy to a diverse array of COF building blocks, ultimately yielding advanced materials tailored for specific applications.
冠醚（CEs）以其卓越的主客体络合作用而闻名，在共价有机框架（COFs）中作为连接体具有潜力，可增强催化和主客体结合性能。然而，它们高度灵活的构象和低对称性限制了基于冠醚的COFs的多样性。在此，我们引入一种新型的C对称氮杂冠醚（ACE）构建单元，即三（吡啶基）[18]冠-6（TPy18C6），用于通过网状合成制备COF（ACE-COF-1和ACE-COF-2）。这种方法能够将冠醚精确整合到COFs中，增强镍离子固定，同时保持结晶度。所得的镍掺杂COFs（Ni@ACE-COF-1和Ni@ACE-COF-2）作为碱性镍锌水系电池的阴极材料，表现出高放电容量（在8 mA·cm时高达1.27 mAh·cm）和出色的循环稳定性（>1000次循环）。本研究是大环化学与网状化学无缝整合的典范，为将大环合成子驱动策略扩展到各种COF构建单元奠定了基础，最终产生针对特定应用定制的先进材料。
