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Porous Self-Assembled Molecular Networks as Templates for Chiral-Position-Controlled Chemical Functionalization of Graphitic Surfaces

  • Kazukuni Tahara*
    Kazukuni Tahara
    Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571, Japan
    Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
    PRESTO, Japan Science and Technology Agency, 4-1-8, Honcho, Kawaguchi, Saitama 332-0012, Japan
    *[email protected]
  • Yuki Kubo
    Yuki Kubo
    Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
    More by Yuki Kubo
  • Shingo Hashimoto
    Shingo Hashimoto
    Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571, Japan
  • Toru Ishikawa
    Toru Ishikawa
    Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
  • Hiromasa Kaneko
    Hiromasa Kaneko
    Department of Applied Chemistry, School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571, Japan
  • Anton Brown
    Anton Brown
    Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
    More by Anton Brown
  • Brandon E. Hirsch
    Brandon E. Hirsch
    Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
  • Steven De Feyter*
    Steven De Feyter
    Division of Molecular Imaging and Photonics, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium
    *[email protected]
  • , and 
  • Yoshito Tobe*
    Yoshito Tobe
    The Institute of Scientific and Industrial Research, Osaka University, Ibaraki, Osaka 567-0047, Japan
    Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
    Department of Applied Chemistry, National Chiao Tung University, 1001 Ta Hsueh Road, Hsinchu 30010, Taiwan
    *[email protected]
    More by Yoshito Tobe
Cite this: J. Am. Chem. Soc. 2020, 142, 16, 7699–7708
Publication Date (Web):March 26, 2020
https://doi.org/10.1021/jacs.0c02979
Copyright © 2020 American Chemical Society

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    Abstract

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    Controlled covalent functionalization of graphitic surfaces with molecular scale precision is crucial for tailored modulation of the chemical and physical properties of carbon materials. We herein present that porous self-assembled molecular networks (SAMNs) act as nanometer scale template for the covalent electrochemical functionalization of graphite using an aryldiazonium salt. Hexagonally aligned achiral grafted species with lateral periodicity of 2.3, 2.7, and 3.0 nm were achieved utilizing SAMNs having different pore-to-pore distances. The unit cell vectors of the grafted pattern match those of the SAMN. After the covalent grafting, the template SAMNs can be removed by simple washing with a common organic solvent. We briefly discuss the mechanism of the observed pattern transfer. The unit cell vectors of the grafted pattern align along nonsymmetry axes of graphite, leading to mirror image grafted domains, in accordance with the domain-specific chirality of the template. In the case in which a homochiral building block is used for SAMN formation, one of the 2D mirror image grafted patterns is canceled. This is the first example of a nearly crystalline one-sided or supratopic covalent chemical functionalization. In addition, the positional control imposed by the SAMN renders the functionalized surface (homo)chiral reaching a novel level of control for the functionalization of carbon surfaces, including surface-supported graphene.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c02979.

    • Experimental details, MM simulations, additional STM images, additional Raman spectra, details of positional analysis, and synthesis of new DBA derivative (PDF)

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    This article is cited by 27 publications.

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    21. Miriam C. Rodríguez González, Kunal S. Mali, Steven De Feyter. Covalent Modification of Graphite and Graphene Using Diazonium Chemistry. 2022, 157-181. https://doi.org/10.1007/978-3-031-04398-7_8
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