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Programmable photocatalytic activity of multivariate covalent organic frameworks used as metallaphotocatalysts

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Reischauer,  Susanne
Bartholomäus Pieber, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society;

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Pieber,  Bartholomäus       
Bartholomäus Pieber, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society;

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Citation

Traxler, M., Reischauer, S., Vogl, S., Roeser, J., Rabeah, J., Penschke, C., et al. (2023). Programmable photocatalytic activity of multivariate covalent organic frameworks used as metallaphotocatalysts. Chemistry – A European Journal, 29(4): e202202967. doi:10.1002/chem.202202967.


Cite as: https://hdl.handle.net/21.11116/0000-000B-487A-C
Abstract
The multivariate 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 multivariate COFs is furthermore ideally suited for structure-activity relationship studies. We report a series of multivariate 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 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. This allows switching between high charge-carrier mobility and persistent, localized charge-separated species depending on the nodes, a tool to tailor the materials for specific reactions. Moreover, nickel-loaded COFs are recyclable and catalyze cross-couplings even using red light irradiation.