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Enantiomeric Separation of Semiconducting Single-Walled Carbon Nanotubes by Acid Cleavable Chiral Polyfluorene
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    Enantiomeric Separation of Semiconducting Single-Walled Carbon Nanotubes by Acid Cleavable Chiral Polyfluorene
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    • Liang Xu
      Liang Xu
      Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
      More by Liang Xu
    • Michal Valášek*
      Michal Valášek
      Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
      *Email: [email protected]
    • Frank Hennrich
      Frank Hennrich
      Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
      Institute of Quantum Materials and Technologies, Karlsruhe Institute of Technology, 76021 Karlsruhe, Germany
    • Elaheh Sedghamiz
      Elaheh Sedghamiz
      Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
    • Montserrat Penaloza-Amion
      Montserrat Penaloza-Amion
      Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
    • Daniel Häussinger
      Daniel Häussinger
      Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland
    • Wolfgang Wenzel
      Wolfgang Wenzel
      Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
    • Manfred M. Kappes*
      Manfred M. Kappes
      Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
      Institute of Quantum Materials and Technologies, Karlsruhe Institute of Technology, 76021 Karlsruhe, Germany
      Institute of Physical Chemistry, Karlsruhe Institute of Technology, 76128 Karlsruhe, Germany
      *Email: [email protected]
    • Marcel Mayor*
      Marcel Mayor
      Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021 Karlsruhe, Germany
      Department of Chemistry, University of Basel, St. Johanns-Ring 19, 4056 Basel, Switzerland
      Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou, Guangdong 510275, China
      *Email: [email protected]
      More by Marcel Mayor
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    ACS Nano

    Cite this: ACS Nano 2021, 15, 3, 4699–4709
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    https://doi.org/10.1021/acsnano.0c09235
    Published February 24, 2021
    Copyright © 2021 American Chemical Society

    Abstract

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    Helical wrapping by conjugated polymer has been demonstrated as a powerful tool for the sorting of single-walled carbon nanotubes (SWCNTs) according to their electronic type, chiral index, and even handedness. However, a method of one-step extraction of left-handed (M) and right-handed (P) semiconducting SWCNTs (s-SWCNTs) with subsequent cleavage of the polymer has not yet been published. In this work, we designed and synthesized one pair of acid cleavable polyfluorenes with defined chirality for handedness separation of s-SWCNTs from as-produced nanotubes. Each monomer contains a chiral center on the fluorene backbone in the 9-position, and the amino and carbonyl groups in the 2- and 7-positions maintain the head-to-tail regioselective polymerization resulting in polyimines with strictly all-(R) or all-(S) configuration. The obtained chiral polymers exhibit a strong recognition ability toward left- or right-handed s-SWCNTs from commercially available CoMoCAT SWCNTs with a sorting process requiring only bath sonication and centrifugation. Interestingly, the remaining polymer on each single nanotube, which helps to prevent aggregation, does not interfere with the circular dichroism signals from the nanotube at all. Therefore, we observed all four interband transition peaks (E11, E22, E33, E44) in the circular dichroism (CD) spectra of the still wrapped optically enriched left-handed and right-handed (6,5) SWCNTs in toluene. Binding energies obtained from molecular dynamics simulations were consistent with our experimental results and showed a significant preference for one specific handedness from each chiral polymer. Moreover, the imine bonds along the polymer chains enable the release of the nanotubes upon acid treatment. After s-SWNT separation, the polymer can be decomposed into monomers and be cleanly removed under mild acidic conditions, yielding dispersant-free handedness sorted s-SWNTs. The monomers can be almost quantitatively recovered to resynthesize the chiral polymer. This approach enables high selective isolation of polymer-free s-SWNT enantiomers for their further applications in carbon nanotube (CNT) devices.

    Copyright © 2021 American Chemical Society

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.0c09235.

    • Monomer and polymer synthesis in detail, characterizations of all molecules, procedure for acid-based triggering of the wrapped SWCNTs, procedure for the redispersion of triggered SWCNTs with achiral polymer, details of the Mosher’s method to determine the absolute configuration of enantiomeric monomers using NMR analysis, additional absorption, Raman, AFM, and XPS results, theoretical calculations of absorption, and CD spectra of enantiomers (PDF)

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    ACS Nano

    Cite this: ACS Nano 2021, 15, 3, 4699–4709
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.0c09235
    Published February 24, 2021
    Copyright © 2021 American Chemical Society

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