Designing a Photoactive Polyoxometalate-Based Metal-Organic Framework for Solar-Powered Hantzsch Reactions in a Divergent and Mild Pathway to Thermal Methods.

Developing a photocatalytic strategy for the multicomponent Hantzsch reaction to construct important nitrogen-containing heterocyclic dihydropyridine compounds under mild conditions is of great significance. This work introduces a new strategy for the solar-driven Hantzsch reaction, leveraging a polyoxometalate-based metal-organic framework (POMOF) as a multifunctional photocatalyst. Unlike conventional thermal approaches, it enables divergent reaction pathways and products under mild ambient conditions, significantly enhancing sustainability and selectivity. Herein, a donor-acceptor structural POMOF, ZnW-TPB, was synthesized from flexible electron-rich TPB photosensitizer, zinc ions, and electron sponge [BW12O40]5- via the solvothermal method. The combination of REDOX [BW12O40]5- into a MOF is conducive to charge separation and electron migration, thus resulting in the generation of superoxide radicals (•O2-) at low oxygen concentrations. •O2- performs the hydrogen abstraction function to remove the H atom from the N-H bond to form stable radical intermediates, which are the key intermediates in the Hantzsch reaction for the synthesis of 1,4-dihydropyridine. Just by simply controlling the reaction time, further oxidation can be achieved to obtain pyridine derivatives.