Construction of Covalent Organic Frameworks with Crown Ether Struts

Abstract Crown ethers are a class of macrocyclic molecules with unique flexible structures but they are rarely integrated in covalent organic frameworks (COFs). To date, employing flexible organic units such as crown ethers to construct COFs with high crystallinity and surface area are still a challenge. In this work, two new COFs with different flexible crown ethers as backbone rather than side chains are synthesized and further employed for alkali metal ions separation. Both of COFs possess high surface areas, good crystallinity, and excellent chemical stability. Interestingly, these two new COFs with 18‐crown‐6 or 24‐crown‐8 units showed remarkable binding ability of K + or Cs + owing to the size‐fit effect. This work demonstrated that the unique structural features of crown ethers will lead to increase interest in fabricating COFs with crown ethers.