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Coordination cage with structural “defects” and open metal sites catalyzes selective oxidation of primary alcohols

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Abstract

Coordination cages with intrinsic enzyme-like activity are a class of promising catalysts for improving the efficiency of organic reactions. We present herein a viable strategy to conveniently construct multimetallic active sites into a coordination cage via self-assembly of a pre-formed sulfonylcalix[4]arene-based tetranuclear copper(II) precursor and an amino-functionalized dicarboxylate linker. The cage exhibits a “defective”, partially open cylindrical structure and features coordinatively labile dimetallic Cu(II) sites. Modulated by this unique inner cavity environment, promising catalytic activity toward selective oxidation of primary alcohols to carboxylic acids at room temperature is achieved. Mechanistic studies reveal that the coordinatively labile dimetallic Cu(II) sites can efficiently capture and activate the substrate and oxidant to catalyze the reaction, while the confined nano-cavity environment modulates substrate binding and enhances the catalytic turnover. This study provides a new approach to designing biomimetic multifunctional coordination cages and environmentally friendly supramolecular catalysts.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21673239, 92061202, U22A20387), the Fujian Science and Technology Project (2020L3022), and the Science and Technology Service Network Initiative (STS) Foundation of Fujian Provincial Department of Science and Technology (2021T3004). Z.W. and P.J. acknowledge the financial support provided by the National Science Foundation (CHE-1800354) and the South Dakota Governor’s Office of Economic Development through the Center for Fluorinated Functional Materials (CFFM).

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Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Tian-Pu Sheng, Chang Li, Feng-Rong Dai & Zhong-Ning Chen

  2. College of Chemistry, Fuzhou University, Fuzhou, 350108, China

    Ying Wei & Shuping Huang

  3. University of Chinese Academy of Sciences, Beijing, 100049, China

    Tian-Pu Sheng, Chang Li, Feng-Rong Dai & Zhong-Ning Chen

  4. Department of Chemistry & Center for Fluorinated Functional Materials, University of South Dakota, Vermillion, SD, USA

    Parvathi Jampani & Zhenqiang Wang

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  1. Tian-Pu Sheng
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  2. Ying Wei
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  3. Parvathi Jampani
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  4. Chang Li
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  5. Feng-Rong Dai
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  6. Shuping Huang
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  8. Zhong-Ning Chen
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Correspondence to Feng-Rong Dai, Shuping Huang, Zhenqiang Wang or Zhong-Ning Chen.

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Conflict of interest The authors declare no conflict of interest.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Sheng, TP., Wei, Y., Jampani, P. et al. Coordination cage with structural “defects” and open metal sites catalyzes selective oxidation of primary alcohols. Sci. China Chem. 66, 1714–1721 (2023). https://doi.org/10.1007/s11426-023-1584-y

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  • DOI: https://doi.org/10.1007/s11426-023-1584-y

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