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Anatomy of On-Surface Synthesized Boroxine Two-Dimensional Polymers

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    Anatomy of On-Surface Synthesized Boroxine Two-Dimensional Polymers
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    • Nerea Bilbao*
      Nerea Bilbao
      Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
      *E-mail: [email protected]
      More by Nerea Bilbao
    • Cristina Martín
      Cristina Martín
      Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
      Departamento de Química Física, Facultad de Farmacia, Universidad de Castilla-La Mancha, 02071 Albacete, Spain
      More by Cristina Martín
      Orcidhttp://orcid.org/0000-0002-7588-8759
    • Gaolei Zhan
      Gaolei Zhan
      Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
      More by Gaolei Zhan
    • Marta Martínez-Abadía
      Marta Martínez-Abadía
      POLYMAT, University of the Basque Country UPV/EHU, Avenida de Tolosa 72, E-20018 Donostia-San Sebastián, Spain
      More by Marta Martínez-Abadía
    • Ana Sanz-Matı́as
      Ana Sanz-Matı́as
      Department of Chemistry, Quantum Chemistry, and Physical Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
      More by Ana Sanz-Matı́as
    • Aurelio Mateo-Alonso
      Aurelio Mateo-Alonso
      POLYMAT, University of the Basque Country UPV/EHU, Avenida de Tolosa 72, E-20018 Donostia-San Sebastián, Spain
      Ikerbasque, Basque Foundation for Science, 48013 Bilbao, Spain
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      Orcidhttp://orcid.org/0000-0002-5316-2594
    • Jeremy N. Harvey
      Jeremy N. Harvey
      Department of Chemistry, Quantum Chemistry, and Physical Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
      More by Jeremy N. Harvey
      Orcidhttp://orcid.org/0000-0002-1728-1596
    • Mark Van der Auweraer
      Mark Van der Auweraer
      Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
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    • Kunal S. Mali*
      Kunal S. Mali
      Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
      *E-mail: [email protected]
      More by Kunal S. Mali
      Orcidhttp://orcid.org/0000-0002-9938-6446
    • Steven De Feyter*
      Steven De Feyter
      Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
      *E-mail: [email protected]
      More by Steven De Feyter
      Orcidhttp://orcid.org/0000-0002-0909-9292
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    ACS Nano

    Cite this: ACS Nano 2020, 14, 2, 2354–2365
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    https://doi.org/10.1021/acsnano.9b09520
    Published February 3, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Synthetic two-dimensional polymers (2DPs) obtained from well-defined monomers via bottom-up fabrication strategies are promising materials that can extend the realm of inorganic 2D materials. The on-surface synthesis of such 2DPs is particularly popular, however the pathway complexity in the growth of such films formed on solid surfaces is poorly understood. In this contribution, we present a straightforward experimental protocol which allows the synthesis of large-area, defect-free 2DPs based on boroxine linkages at room temperature. We focus on unravelling the multiple pathways available to the polymerizing system for the spatial extension of the covalent bonds. Besides the anticipated 2DP, the system can evolve into self-assembled monolayers of partially fused monodisperse reaction products that are difficult to isolate by conventional synthetic methods or remain in the monomeric state. The access to each pathway can be controlled via monomer concentration and the choice of the solvent. Most importantly, the unpolymerized systems do not evolve into the corresponding 2DP upon annealing, indicating the presence of strong kinetic traps. Using high-resolution scanning tunneling microscopy, we show reversibility in the polymerization process where the attachment and the detachment of monomers to 2DP crystallites could be monitored as a function of time. Finally, we show that the way the 2DP grows depends on the choice of the solvent. Using UV–vis absorption and emission spectroscopy, we reveal that the dominant pathway for 2DP growth is via in-plane self-condensation of the monomers, whereas in the case of an aprotic solvent, the favored growth mode is via π stacking of the monomers.

    Copyright © 2020 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/acsnano.9b09520.

    • Experimental details and additional data; STM images; UV−vis, and IR spectra (PDF)

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    Cited By

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    This article is cited by 16 publications.

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    2. Chunyang Bao, Ruoxuan Miao, Yanlong Yin, Yang Xu, Yuhan Ding, Jie Liu, Zhirong Xin. Mechanically Robust yet Body-Temperature Self-Healable Polyurethane Elastomer via the Cross-Linking of Dynamic Boroxines. ACS Applied Polymer Materials 2024, 6 (1) , 797-805. https://doi.org/10.1021/acsapm.3c02418
    3. Zhen-Feng Cai, Ting Chen, Dong Wang. Insights into the Polymerization Reactions on Solid Surfaces Provided by Scanning Tunneling Microscopy. The Journal of Physical Chemistry Letters 2023, 14 (10) , 2463-2472. https://doi.org/10.1021/acs.jpclett.2c03943
    4. Mina Moradi, Nadia L. Lengweiler, Catherine E. Housecroft, Ludovico G. Tulli, Henning Stahlberg, Thomas A. Jung, Patrick Shahgaldian. Coordination-Driven Monolayer-to-Bilayer Transition in Two-Dimensional Metal–Organic Networks. The Journal of Physical Chemistry B 2021, 125 (16) , 4204-4211. https://doi.org/10.1021/acs.jpcb.1c01058
    5. Xiaonan Sun, Xinlei Yao, Gaelle Trippé-Allard, Jean-Christophe Lacroix. On-Surface Dimerization and Coordination of 4-(Bis-ethylenedioxythiophene)benzoic Acid. The Journal of Physical Chemistry C 2021, 125 (1) , 957-963. https://doi.org/10.1021/acs.jpcc.0c08522
    6. Huifang Li, Hong Li, Sangni Xun, Jean-Luc Brédas. Doping Modulation of the Charge Injection Barrier between a Covalent Organic Framework Monolayer and Graphene. Chemistry of Materials 2020, 32 (21) , 9228-9237. https://doi.org/10.1021/acs.chemmater.0c02913
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    ACS Nano

    Cite this: ACS Nano 2020, 14, 2, 2354–2365
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.9b09520
    Published February 3, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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