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Decafluorinated and Perfluorinated Warped Nanographenes: Synthesis, Structural Analysis, and Properties
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    Decafluorinated and Perfluorinated Warped Nanographenes: Synthesis, Structural Analysis, and Properties
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    • Xue-Peng Zhang
      Xue-Peng Zhang
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
    • Si-Wei Ying
      Si-Wei Ying
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
      More by Si-Wei Ying
    • Yi-Lu Zhang
      Yi-Lu Zhang
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
      More by Yi-Lu Zhang
    • Wen-Xin Zhang
      Wen-Xin Zhang
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
    • Wenjie Shi
      Wenjie Shi
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
      More by Wenjie Shi
    • Bin-Wen Chen
      Bin-Wen Chen
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
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    • Han-Rui Tian
      Han-Rui Tian
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
      More by Han-Rui Tian
    • Gan Xu
      Gan Xu
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
      More by Gan Xu
    • Shan-Shan Wang
      Shan-Shan Wang
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
    • Qianyan Zhang*
      Qianyan Zhang
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
      *Email: [email protected]
    • Su-Yuan Xie
      Su-Yuan Xie
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
      More by Su-Yuan Xie
    • Lan-Sun Zheng
      Lan-Sun Zheng
      State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen 361005, China
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2024, 146, 45, 30913–30921
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    https://doi.org/10.1021/jacs.4c09373
    Published October 5, 2024
    Copyright © 2024 American Chemical Society

    Abstract

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    Fluorination is a useful approach for tailoring the physicochemical properties of nanocarbon materials. However, owing to the violent reactivity of fluorination, achieving edge-perfluorination of nanographene while maintaining its original π-conjugated structure is challenging. Instead of using traditional fluorination, here, we employed a bottom-up strategy involving fluorine preinstallation and synthesized decafluorinated and perfluorinated warped nanographenes (DFWNG and PFWNG, respectively) through a 10-fold Suzuki–Miyaura coupling followed by a harsh Scholl reaction, whereby precisely edge-perfluorinated nanographene with an intact π-conjugated structure was achieved for the first time. X-ray crystallography confirmed the intact π-conjugated structure and more twisted saddle-shaped geometry of PFWNG compared to that of DFWNG. Dynamic study revealed that the 26-ring carbon framework of PFWNG is less flexible than that of DFWNG and the pristine WNG, enabling chirality resolution of PFWNG and facilitating the achievement of CD spectra at −10 °C. The edge-perfluorination of PFWNG resulted in improved solubility, lower lowest unoccupied molecular orbital, and a surface electrostatic potentials/dipole moment direction opposite those of the pristine WNG. Likely owing to its intact π-conjugated structure, PFWNG exhibits comparable electron mobility with well-known PC61BM. Furthermore, perfluorination improves thermal stability and hydrophobicity, making PFWNG suitable for use as a thermostable/hydrophobic n-type semiconductor material. In the future, this fluorination strategy can be used to synthesize other perfluorinated nanocarbon materials, such as perfluorinated graphene nanoribbons and porous nanocarbon.

    Copyright © 2024 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.4c09373.

    • Experimental methods, detailed synthesis and additional data, 1H and 13C NMR spectra, and mass spectra (PDF)

    Accession Codes

    Accession Codes CCDC 2246371 and 2246438 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2024, 146, 45, 30913–30921
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.4c09373
    Published October 5, 2024
    Copyright © 2024 American Chemical Society

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