A flavin-inspired covalent organic framework for photocatalytic alcohol oxidation

Covalent organic frameworks (COFs) offer a number of key properties that predestine them to be used as heterogeneous photocatalysts, including intrinsic porosity, long-range order, and light absorption. Since COFs can be constructed from a practically unlimited library of organic building blocks, these properties can be precisely tuned by choosing suitable linkers. Herein, we report the construction and use of a novel COF (FEAx-COF) photocatalyst, inspired by natural flavin cofactors. We show that the functionality of the alloxazine chromophore incorporated into the COF backbone is retained and study the effects of this heterogenization approach by comparison with similar molecular photocatalysts. We find that the integration of alloxazine chromophores into the framework significantly extends the absorption spectrum into the visible range, allowing for photocatalytic oxidation of benzylic alcohols to aldehydes even with low-energy visible light. In addition, the activity of the heterogeneous COF photocatalyst is less dependent on the chosen solvent, making it more versatile compared to molecular alloxazines. Finally, the use of oxygen as the terminal oxidant renders FEAx-COF a promising and green heterogeneous photocatalyst.

Automated summary

COFs, as heterogeneous photocatalysts, possess intrinsic porosity, long-range order, and light absorption, with properties that can be precisely tuned by choosing suitable linkers. The novel COF photocatalyst presented in the study can catalyze oxidation reactions under visible light, showing less dependence on solvent choice compared to molecular catalysts. Utilizing oxygen as the terminal oxidant makes FEAx-COF a promising and environmentally friendly photocatalyst.