Luo Tian, Jeppesen Henrik S, Schoekel Alexander, Bönisch Nadine, Xu Fei, Zhuang Rong, Huang Qiang, Senkovska Irena, Bon Volodymyr, Heine Thomas, Kuc Agnieszka, Kaskel Stefan
Chair of Inorganic Chemistry I, Technische Universität Dresden, Bergstr. 66, 01069, Dresden, Germany.
Deutsches Elektronensynchrotron DESY, Notkestr. 85, 22607, Hamburg, Germany.
Angew Chem Int Ed Engl. 2025 Mar 24;64(13):e202422776. doi: 10.1002/anie.202422776. Epub 2025 Jan 13.
The catalytic potential of flexible metal-organic frameworks (MOFs) remains underexplored, particularly in liquid-phase reactions. This study employs MIL-53(Cr), a prototypical "breathing" MOF capable of structural adaptation via pore size modulation, as a photocatalyst for the dehalogenation of aryl halides. Powder X-ray diffraction and Pair Distribution Function analyses reveal that organic solvents influence pore opening, while substrates and products dynamically adjust the framework configuration during catalysis. This structural flexibility enables precise tuning of photocatalytic efficiency via solvent-mediated control of the pore aperture. The results demonstrate that the dynamic behavior of MIL-53(Cr) facilitates enhanced catalytic activity and selectivity, advancing the application of flexible MOFs as tunable, enzyme-mimicking catalysts. These findings pave the way for the rational design of next-generation flexible photocatalysts.
柔性金属有机框架材料（MOFs）的催化潜力尚未得到充分探索，尤其是在液相反应中。本研究采用MIL-53（Cr），一种能够通过孔径调节实现结构适配的典型“呼吸”MOF，作为芳基卤化物脱卤反应的光催化剂。粉末X射线衍射和对分布函数分析表明，有机溶剂会影响孔的打开，而底物和产物在催化过程中会动态调整框架结构。这种结构灵活性使得通过溶剂介导的孔径控制能够精确调节光催化效率。结果表明，MIL-53（Cr）的动态行为有助于提高催化活性和选择性，推动了柔性MOFs作为可调谐、模拟酶催化剂的应用。这些发现为下一代柔性光催化剂的合理设计铺平了道路。
