Aqueous-Phase Synthesis of Cyclic Trinuclear Cluster-Based Metal–Organic Frameworks

作者：Kun Wu, Wei Zhao, Ling Huang, Wenting Zeng, Qiang Zhu, Haobo Wang, Qinhong Wang, Xiansong Shi, He Li, Weigang Lu, Guo‐Hong Ning, Dan Zhao, Dan Li · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c01434 · 被引用次数：33 · 研究领域：Metal-Organic Frameworks: Synthesis and Applications、Nanocluster Synthesis and Applications、Magnetism in coordination complexes

The synthesis of metal–organic frameworks (MOFs) often involves high-boiling-point organic solvents, which can have extensive environmental impact and limit their large-scale applications. Here, we present a one-pot aqueous-phase approach for the rapid preparation of 33 trinuclear-copper-cluster-based MOFs ( 1 to 33 ) with different pyrazoles under ultrasonic irradiation. To address the water-solubility challenge of organic linkers, we employ aromatic amines/aldehydes and pyrazole aldehydes/amines to in situ generate imine-based pyrazoles. This linker dismantling strategy enables the formation of low-concentration pyrazoles, which are essential for the assembly of trinuclear-copper-cluster-based MOFs in the aqueous phase. The use of preassembled trinuclear gold complexes instead of aromatic amines affords an Au–Cu-based MOF ( 34 ) of alternating gold and copper clusters, a rare example of MOFs with mixed yet precise arrangement of metal compositions. Additionally, the direct addition of pyruvic acid to the reaction mixture results in the facile synthesis of a carboxylic-acid-functionalized MOF ( 35 ), eliminating the need for preinstallation or postmodification steps in traditional MOF synthesis. Furthermore, we demonstrate 11-AA as an efficient photocatalyst for cross-dehydrogenative coupling (CDC) reactions, exploiting the synergetic effect of substrate activation on the copper sites and subsequent coupling initiated by the photosensitive organic linkers. This work offers a...