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Deciphering the factors influencing electric field mediated polymerization and depolymerization at the solution-solid

Zhinan Fu1, Nicolás Arisnabarreta1, Kunal S Mali2

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Summary
This summary is machine-generated.

Strong electric fields (EF) reversibly control 2D polymerization of aryl boronic acids on graphite. Switching polarity of the scanning tunneling microscope tip bias drives depolymerization and monomer desorption, influencing molecular self-assembly.

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Area of Science:

  • Surface science
  • Nanotechnology
  • Materials chemistry

Background:

  • Strong electric fields (EF) influence molecular structure and reactivity.
  • Scanning tunneling microscopy (STM) can probe and manipulate molecular assemblies at the nanoscale.
  • Two-dimensional polymers (2DPs) offer unique properties for advanced materials.

Purpose of the Study:

  • To investigate the factors governing electric field-mediated polymerization and depolymerization of boroxine-based 2DPs on graphite.
  • To understand the role of solvent polarity and monomer concentration in EF-driven 2D polymerization.
  • To elucidate the mechanism behind the reversible transition between monomer networks and 2DP domains.

Main Methods:

  • Utilized scanning tunneling microscopy (STM) to apply electric fields to aryl boronic acid monomers on a graphite surface.
  • Systematically varied solvent properties (polar protic, polar aprotic, non-polar) to assess their influence.
  • Investigated the effect of monomer concentration and time-dependence on the polymerization process.

Main Results:

  • Electric field (EF) does not initiate nucleation of 2D polymer (2DP) domains.
  • Depolymerization and subsequent monomer desorption are triggered by polarity changes in the substrate bias.
  • The reversible transition between monomer networks and 2DP domains is linked to bias-induced monomer adsorption/desorption.

Conclusions:

  • The reversible 2D polymerization of boroxine-based systems on graphite is controllable via electric field polarity.
  • Bias-induced adsorption and desorption of monomers are key mechanisms driving the observed reversible transitions.
  • Local monomer concentration changes, influenced by adsorption/desorption, play a critical role in EF-mediated (de)polymerization.