He Xinglei, Yu Chunlong, Zhang Fengtao, Gong Chenxu, Li Jingheng, Zeng Ding-Bo, Zhao Bin, Chen Xiong, Ye Ke-Yin
Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou, 350108, China.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, 453007, China.
Adv Sci (Weinh). 2025 Sep;12(33):e06037. doi: 10.1002/advs.202506037. Epub 2025 Jun 5.
Metal-organic frameworks (MOFs) composed of infinite metal units exhibit enhanced electron transport and charge migration capabilities compared to discrete metal units. Herein, three underdeveloped isomorphic MOFs featuring 3D infinite zinc units are designed and synthesized. The Lewis acidity and photocatalytic activity of these MOFs are fine-tuned through atomic-level engineering of nitrogen atoms of ligands and the resultant change of charge transfer modes. These MOFs are promising catalysts in the photocatalytic monooxygenation of sulfenamides with molecular oxygen. Mechanistic investigations suggest that the uneven charge distribution and large dipole moment at the pyridine center of 1-PTB and the infinite Zn unit frameworks of degenerate energy levels are key to its excellent photocatalytic activity.
与离散金属单元相比，由无限金属单元组成的金属有机框架（MOF）展现出增强的电子传输和电荷迁移能力。在此，设计并合成了三种具有三维无限锌单元的未充分开发的同构MOF。通过配体氮原子的原子级工程以及电荷转移模式的相应变化，对这些MOF的路易斯酸度和光催化活性进行了微调。这些MOF是用分子氧光催化亚磺酰胺单加氧反应中有前景的催化剂。机理研究表明，1-PTB吡啶中心的电荷分布不均和大偶极矩以及简并能级的无限锌单元框架是其优异光催化活性的关键。
