Programmable Photocatalytic Activity of Multicomponent Covalent Organic Frameworks Used as Metallaphotocatalysts

The multicomponent approach allows to incorporate several functionalities into a single covalent organic framework (COF) and consequently allows the construction of bifunctional materials for cooperative catalysis. The well‐defined structure of such multicomponent COFs is furthermore ideally suited for structure‐activity relationship studies. We report a series of multicomponent COFs that contain acridine‐ and 2,2’‐bipyridine linkers connected through 1,3,5‐benzenetrialdehyde derivatives. The acridine motif is responsible for broad light absorption, while the bipyridine unit enables complexation of nickel catalysts. These features enable the usage of the framework materials as catalysts for light‐mediated carbon−heteroatom cross‐couplings. Variation of the node units shows that the catalytic activity correlates to the keto‐enamine tautomer isomerism.