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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Thermal- vs Light-Induced On-Surface Polymerization.

Christophe Nacci1, Monika Schied1, Donato Civita1

  • 1Department of Physical Chemistry, University of Graz, 8010 Graz, Austria.

The Journal of Physical Chemistry. C, Nanomaterials and Interfaces
|October 29, 2021
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Summary
This summary is machine-generated.

Comparing thermal and light-induced on-surface polymerization of dibromo-anthracene reveals distinct outcomes. Thermal methods yield longer polymers with increasing temperature, while light primarily forms short structures, influenced by molecular diffusion.

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Area of Science:

  • Surface science
  • Materials chemistry
  • Polymer chemistry

Background:

  • On-surface polymerization enables bottom-up synthesis of covalent structures on single-crystal surfaces.
  • Thermal initiation, often via halogen cleavage, is common, while light initiation is less explored.
  • Dibromo-anthracene is a model system for studying polymerization mechanisms.

Purpose of the Study:

  • To directly compare thermal and light-induced on-surface polymerization of dibromo-anthracene.
  • To elucidate the differences in polymer formation and characteristics between the two initiation methods.
  • To investigate the influence of temperature and light on polymerization outcomes.

Main Methods:

  • Scanning tunneling microscopy (STM) for local analysis of polymer shape and size.
  • X-ray photoelectron spectroscopy (XPS) for average bond formation analysis.
  • Controlled thermal heating and UV light irradiation of dibromo-anthracene on a surface.

Main Results:

  • Thermal polymerization length increases with heating temperature.
  • Light-induced polymerization predominantly forms short covalent structures, irrespective of light exposure duration.
  • UV irradiation at varying temperatures highlights the critical role of molecular diffusion in polymerization.

Conclusions:

  • Thermal and light-induced on-surface polymerization pathways for dibromo-anthracene yield significantly different polymer lengths.
  • Light initiation is less effective for growing long polymer chains compared to thermal methods.
  • Molecular diffusion is a key factor influencing polymerization outcomes under light irradiation.