Engineering Bodipy-Based Metal-Organic Frameworks for Efficient Full-Spectrum Photocatalysis in Amide Synthesis.

Developing photocatalysts that can efficiently utilize the full solar spectrum is a crucial step toward transforming sustainable energy solutions. Due to their light absorption limitations, most photo-responsive metal-organic frameworks (MOFs) are constrained to the ultraviolet (UV) and blue light regions. Expanding their absorption to encompass the entire solar spectrum would unlock their full potential, greatly enhancing efficiency and applicability. Here, we report the design and synthesis of a series of highly stable boron-dipyrromethene (bodipy)-based MOFs (BMOFs) by reacting dicarboxyl-functionalized bodipy ligands with Zr-oxo clusters. Leveraging the acidity of the methyl groups on the bodipy backbone, we expanded the conjugation system through a solid-state condensation reaction with various aldehydes, achieving full-color absorption, thereby extending the band edge into the near-infrared (NIR) and infrared (IR) regions. These BMOFs demonstrated exceptional reactivity and recyclability in heterogeneous photocatalytic activities, including C─H bond activation of saturated aza-heterocycles and C─N bond cleavage of N,N-dimethylanilines to produce amides under visible light. Our findings highlight the transformative potential of BMOFs in photocatalysis, marking a significant leap forward in the design of advanced photocatalytic materials with tunable properties.