Sustainable and Bench‐Stable Photoactive Aqueous Nanoaggregates of Cu(II) for ppm Level Cu(I) Catalysis in Water
Sustainable and Bench‐Stable Photoactive Aqueous Nanoaggregates of Cu(II) for ppm Level Cu(I) Catalysis in Water
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DOI：
10.1002/adfm.202204459
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发表时间：
2022-06
影响因子：
19
通讯作者：
Sudripet Sharma;S. Parmar;F. Ibrahim;A. Clark;M. Nachtegaal;J. Jasinski;F. Gallou;P. Kozlowski;Sachin Handa
中科院分区：
文献类型：
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作者：
Sudripet Sharma;S. Parmar;F. Ibrahim;A. Clark;M. Nachtegaal;J. Jasinski;F. Gallou;P. Kozlowski;Sachin Handa
开发了含有两亲物稳定的单核Cu（II）的纳米材料。该材料通过各种光谱技术进行表征，例如X射线吸收光谱（XAS）、高分辨率透射电子显微镜、核磁共振（NMR）、紫外维斯和红外光谱。由于两亲物结合的Cu（II）中心的结构数据不可用，因此采用基于DFT计算的理论模型。基于NMR光谱数据的分析，包括同位素标记，支持两亲物的叔酰胺基团结合到Cu表面。同样，XAS光谱发现的键距与理论模型一致。时间依赖性DFT研究预测，低激发态具有主导的配体-金属电荷转移（LMCT）特征。Cu（II）在可见光照射下通过LMCT激发辅助变为Cu（I），产生稳健的催化活性物质。研究了该催化剂在水相中对多米诺叠氮-[3+2]环加成反应的催化活性。催化方案适用于各种基材，催化材料在环境条件下稳定长达三个月。
The nanomaterial containing amphiphile‐stabilized mononuclear Cu(II) is developed. The material is characterized by various spectroscopic techniques, such as X‐ray absorption spectrscopy (XAS), high‐resolution transmission electron microscopy, nuclear magnetic resonance (NMR), UV‐vis, and infrared spectroscopies. Since the structural data for the amphiphile‐bound Cu(II) center is not available, a theoretical model based on DFT calculations is employed. The analyses based on NMR spectroscopic data, including the isotope labeling, support that the tertiary amide group of the amphiphile binds to the Cu surface. Likewise, the bond distances found by XAS spectroscopy agree with the theoretical model. Time‐dependent DFT studies predict that the low‐lying excited state has a dominant ligand‐to‐metal charge transfer (LMCT) character. Cu(II) changes to Cu(I) assisted by the LMCT excitation upon visible light irradiation, generating robust catalytically active species. The catalytic activity for domino azidation‐[3+2] cycloaddition reactions in water is investigated. The catalytic protocol is applicable on various substrates, and the catalytic material is stable under ambient conditions for up to three months.