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

作者：Lei Zhang, Jiachen Jiao, Haina Hu, Hui Sun, Xiaoyang Li, Chuan-Bao Zhang, Qiuxia Han · 发表于：Inorganic Chemistry · 年份：2025 · DOI：10.1021/acs.inorgchem.5c03170 · 被引用次数：4 · 研究领域：Polyoxometalates: Synthesis and Applications、Pigment Synthesis and Properties、Metal-Organic Frameworks: Synthesis and Applications

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 [BW 12 O 40 ] 5– via the solvothermal method. The combination of REDOX [BW 12 O 40 ] 5– into a MOF is conducive to charge separation and electron migration, thus resulting in the generation of superoxide radicals ( • O 2 – ) at low oxygen concentrations. • O 2 – 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.