Enhanced Energy Transfer in A π‐Conjugated Covalent Organic Framework Facilitates Excited‐State Nickel Catalysis

Abstract Covalent organic frameworks (COFs) have received broad interest owing to their permanent porosity, high stability, and tunable functionalities. COFs with long‐range π‐conjugation and photosensitizing building blocks have been explored for sustainable photocatalysis. Herein, we report the first example of COF‐based energy transfer Ni catalysis. A pyrene‐based COF with sp 2 carbon‐conjugation was synthesized and used to coordinate Ni II centers through bipyridine moieties. Under light irradiation, enhanced energy transfer in the COF facilitated the excitation of Ni centers to catalyze borylation and trifluoromethylation reactions of aryl halides. The COF showed two orders of magnitude higher efficiency in these reactions than its homogeneous control and could be recovered and reused without significant loss of catalytic activity.