Constructing Functional Radiation-Resistant Thorium Clusters for Catalytic Redox Reactions

作者：Qian Niu, Tao‐Yuan Yu, Jingwen Shi, Qing Huang, Long‐Zhang Dong, Fei Yu, Shun‐Li Li, Jiang Liu, Ya‐Qian Lan · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c03126 · 被引用次数：28 · 研究领域：Catalytic Processes in Materials Science、Catalysis and Oxidation Reactions、Asymmetric Hydrogenation and Catalysis

When catalytic reactions are interfered with by radiation sources, thorium clusters are promising as potential catalysts due to their superior radiation resistance. However, there is currently very little research on the design synthesis and catalytic application of radiation-stable thorium clusters. In this work, we have elaborately engineered and fabricated three high-nuclear thorium cluster catalysts denoted as Th 12 L 3 -MA 12, Th 12 L 3 -MA 6 -BF 6, and Th 12 L 3 -Fcc 12, which did not undergo any significant alterations in their molecular structures and compositions after irradiation with 690 kGy γ-rays. We systematically investigated the photocatalytic/thermocatalytic properties of these radiation-resistant thorium clusters for the first time and found that γ-rays could not alter their catalytic activities. In addition, it was found that ligand engineering could modulate the catalytic activity of thorium clusters, thus expanding the range of catalytic applications of thorium clusters, including reduction reactions (nitroarene reduction) and some oxidation reactions (N-heterocyclic oxidative dehydrogenation and diphenylmethane oxidation). Meanwhile, all of these organic transformation reactions achieved a >80% conversion and nearly 100% product selectivity. Radiation experiments combined with DFT calculations showed that the synergistic catalysis of thorium-oxo core and ligands led to the generation of specific active species (H +, O 2 •–, or t BuO/ t BuOO • ) and activ...