Azine‐Pyridine Frame Generated Covalent Organic Frameworks and Self‐polymerized Films

Engineering covalent organic frameworks (COFs) into industrializable films with inherently functionalities has remained a major challenge in synthetic chemistry. Here, through developing skeletal azine‐pyridine conformation, we present an effectual synthetic frame to conduct a family of powdery COFs into self‐polymerized COFs films under green and ambient conditions. The active proton tautomerism in our azine‐pyridine frame offers a thermochromism, facilitating self‐polymerization of large‐area COFs films from ca. 10 nm to > 30 µm thickness with outstanding chemical stability, industrializable processability, and mechanical strength. More remarkably, our azine‐pyridine based COFs first display various fresh properties, i.e., up to 1913 and 624 mg g−1, reducing capacity on ions of Au3+→Au0 and Cr6+→Cr3+, 99.9% UV‐blue light shielding and 97.2% transmissivity of visible lights, and 10‐folds increase of Zn battery lifetime. We expect that the azine‐pyridine synthetic frame will serve as a generalizable route to boost the development of reticular chemistry, environmental science, and nano‐electronics.