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Anatomy of On-Surface Synthesized Boroxine Two-Dimensional Polymers

  • 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
  • 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
  • Ana Sanz-Matı́as
    Ana Sanz-Matı́as
    Department of Chemistry, Quantum Chemistry, and Physical Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
  • 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
  • Jeremy N. Harvey
    Jeremy N. Harvey
    Department of Chemistry, Quantum Chemistry, and Physical Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
  • 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
  • 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]
  • , and 
  • 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]
Cite this: ACS Nano 2020, 14, 2, 2354–2365
Publication Date (Web):February 3, 2020
https://doi.org/10.1021/acsnano.9b09520
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.

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

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    Cited By

    This article is cited by 12 publications.

    1. 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
    2. 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
    3. 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
    4. 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
    5. Gaolei Zhan, Zhen-Feng Cai, Marta Martínez-Abadía, Aurelio Mateo-Alonso, Steven De Feyter. Real-Time Molecular-Scale Imaging of Dynamic Network Switching between Covalent Organic Frameworks. Journal of the American Chemical Society 2020, 142 (13) , 5964-5968. https://doi.org/10.1021/jacs.0c01270
    6. Qiu Liang, Guangyuan Feng, Hongzhen Ni, Yaru Song, Xinyu Zhang, Shengbin Lei, Wenping Hu. Room temperature spontaneous surface condensation of boronic acids observed by scanning tunneling microscopy. Chinese Chemical Letters 2023, 34 (8) , 108006. https://doi.org/10.1016/j.cclet.2022.108006
    7. Jiang Peng, Xiaochao Dai, Jing Huang, Junqing Zeng, Liping Zheng, Huajie Chen. High-yield preparation of B/N co-doped porous carbon nanosheets from a cross-linked boronate polymer for supercapacitor applications. Journal of Energy Storage 2023, 59 , 106498. https://doi.org/10.1016/j.est.2022.106498
    8. Joshua S. Roys, Jennifer M. O'Brien, Nicholas D. Stucchi, Gaurav Raj, Adam D. Hill, Jingyun Ye, Ryan D. Brown. Enhanced Crystallinity of Covalent Organic Frameworks Formed Under Physical Confinement by Exfoliated Graphene. Small 2022, 18 (46) https://doi.org/10.1002/smll.202204152
    9. Gaolei Zhan, Zhen-Feng Cai, Karol Strutyński, Lihua Yu, Niklas Herrmann, Marta Martínez-Abadía, Manuel Melle-Franco, Aurelio Mateo-Alonso, Steven De Feyter. Observing polymerization in 2D dynamic covalent polymers. Nature 2022, 603 (7903) , 835-840. https://doi.org/10.1038/s41586-022-04409-6
    10. Daniil Naberezhnyi, SangWook Park, Wei Li, Michael Westphal, Xinliang Feng, Renhao Dong, Petr Dementyev. Mass Transfer in Boronate Ester 2D COF Single Crystals. Small 2021, 17 (52) https://doi.org/10.1002/smll.202104392
    11. Chenyu Li, Gui Yu. Controllable Synthesis and Performance Modulation of 2D Covalent–Organic Frameworks. Small 2021, 17 (47) https://doi.org/10.1002/smll.202100918
    12. Brent Daelemans, Nerea Bilbao, Wim Dehaen, Steven De Feyter. Carbocatalysis with pristine graphite: on-surface nanochemistry assists solution-based catalysis. Chemical Society Reviews 2021, 50 (4) , 2280-2296. https://doi.org/10.1039/D0CS01294G

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