Covalent organic frameworks (COFs) as metal-free photocatalysts have attracted extensive interest. However, the organic transformations photocatalyzed by COFs under mild conditions remain a challenge. Herein, a boron-dipyrromethene (BODIPY) based 1D COF, namely JNM-12, was facilely constructed by Schiff-base condensation reaction. JNM-12 exhibited strong visible-light harvesting abilities and suitable photocatalysis energy potentials, enabling the activation of O to superoxide anions (O ⋅ ) and singlet oxygen ( O ) under visible light irradiation. Benefiting from these properties, JNM-12 delivered excellent photocatalytic activity in the O ⋅ -mediated oxidative coupling of amines and O -engaged aerobic oxidation of enamines. Our work paves a new way for synthesis of COFs as efficient, economical, and green photocatalysts for organic synthesis.
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