A Giant Ce3+-Bridged Selenotungstate Containing Three Different Building Blocks for Photocatalyzed C–N Bonds Formation

作者：Yufeng Liu, Jiawei Cao, Jun Wu, Haoqi Liu, Ke Li, Xiao‐Ling Lin, Guo‐Ping Yang · 发表于：Inorganic Chemistry · 年份：2025 · DOI：10.1021/acs.inorgchem.5c01101 · 被引用次数：11 · 研究领域：Polyoxometalates: Synthesis and Applications、Advanced Photocatalysis Techniques、Metal-Organic Frameworks: Synthesis and Applications

The quest to delve into high-nuclearity molecular metal-oxo clusters and unravel their reactivity presents a significant challenge in chemistry and materials science. In this work, we synthesized an unprecedented bowknot-like selenotungstates, [Ce 7 Se 7 W 47 O 171 (OH)(H 2 O) 25 (mal)] 2 30- ( Ce 14 W 94, H 3 mal = dl -malic acid) via an in situ assembly strategy. The three building units, including tetravacant Keggin-{SeW 8 }, bivacant Dawson-{Se 2 W 16 }, and trivacant Keggin-{SeW 9 }, were self-assembled by the connection of {W 1 }, independent {SeO 3 } fragments, and seven mutually isolated Ce 3+ ions to form the unique asymmetric structure, which was further extended to the bowknot-like dimeric structure and the 1D chain structure by symmetry. Due to the good photoelectric activity, Ce 14 W 94 can serve as a highly efficient photocatalyst for the conversion of C–H to C–N bonds by hydroacylation of dialkyl azodicarboxylates, with a broad substrate scope and excellent reusability. This work enriches the assembly mode of POMs and provides a highly efficient photocatalyst.