Photocatalytic Hydroxylation and Oxidative Coupling Reactions Mediated by Multinuclear Au(I) Supramolecular Clusters

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Qing-Ya Sun, Hui-Zhen He, Ying Zhou, Yu-Peng Dai, Ping Shang, Dr. Xuan-Feng Jiang
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Abstract

Polynuclear Au(I) cluster photocatalysts, known for their high activity and stability, hold substantial potential in organic synthetic chemistry. This study synthesized two Au(I) supramolecular cluster catalysts with different nuclearities: a tetranuclear cluster, C1 ([(dppmAu2)2L1] • PF6), and a hexadecanuclear cluster, C2 [(dppmAu2)6(Au4)(L1)4] • 4PF6, through a multicomponent stepwise self-assembly approach. Both cluster structures feature aurophilicity interaction motifs that endow them with exceptional photocatalytic performance, exhibiting optical band gaps of 2.27 eV and 2.41 eV, respectively. Upon photoexcitation, these clusters efficiently generate reactive oxygen species, significantly enhancing their photocatalytic efficacy for the oxidative hydroxylation of phenylboronic acids and oxidative coupling of benzylamines under mild conditions. Catalytic efficiencies exceeding 90 % were achieved. Turnover frequencies for C2 and C1 were measured at 52.045 h−1 and 6.030 h−1, respectively, representing the highest efficiencies reported for photocatalysts to date. Compared to C1, C2 exhibited superior photocatalytic activity, attributed to its higher photoelectric sensitivity and greater exposure of active metal sites. Using a combination of experimental data and density functional theory calculations, the plausible mechanisms were proposed for two photocatalytic reactions. This study demonstrates that the use of multicomponent cooperative self-assembly strategy to synthesize high-nuclearity Au(I) clusters offers innovative pathways for the development of efficient, green, light-driven organic synthesis.

Abstract Image

多核Au(I)超分子团簇介导的光催化羟基化和氧化偶联反应
多核金(I)团簇光催化剂以其高活性和稳定性而闻名,在有机合成化学中具有巨大的潜力。本研究通过多组分逐步自组装方法合成了两种不同核性质的Au(I)超分子团簇催化剂:四核团簇C1 ([(dppmAu2)2L1]•PF6 - 1)和六核团簇C2 [(dppmAu2)6(Au4)(L1)4]•4PF6 - 2。这两种团簇结构都具有亲水性相互作用基元,使其具有优异的光催化性能,分别具有2.27 eV和2.41 eV的光学带隙。在光激发下,这些团簇有效地产生活性氧,在温和条件下显著增强了它们对苯硼酸氧化羟基化和苄胺氧化偶联的光催化效果。催化效率达到90%以上。C2和C1的转换频率分别为52.045 h‐1和6.030 h‐1,这是迄今为止报道的光催化剂的最高效率。与C1相比,C2表现出更强的光催化活性,这是由于其更高的光电灵敏度和更多的活性金属位点暴露。结合实验数据和密度泛函理论计算,提出了两种光催化反应的合理机理。该研究表明,利用多组分协同自组装策略合成高核金(I)簇为开发高效、绿色、光驱动有机合成提供了创新途径。
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来源期刊
CiteScore
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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