Micrometre-long covalent organic fibres by photoinitiated chain-growth radical polymerization on an alkali-halide surface

Nature Chemistry
Franck ParaMatthew B Watkins

Abstract

On-surface polymerization is a promising technique to prepare organic functional nanomaterials that are challenging to synthesize in solution, but it is typically used on metal substrates, which play a catalytic role. Previous examples on insulating surfaces have involved intermediate self-assembled structures, which face high barriers to diffusion, or annealing to higher temperatures, which generally causes rapid dewetting and desorption of the monomers. Here we report the photoinitiated radical polymerization, initiated from a two-dimensional gas phase, of a dimaleimide monomer on an insulating KCl surface. Polymer fibres up to 1 μm long are formed through chain-like rather than step-like growth. Interactions between potassium cations and the dimaleimide's oxygen atoms facilitate the propagation of the polymer fibres along a preferred axis of the substrate over long distances. Density functional theory calculations, non-contact atomic force microscopy imaging and manipulations at room temperature were used to explore the initiation and propagation processes, as well as the structure and stability of the resulting one-dimensional polymer fibres.

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Citations

Apr 11, 2019·Journal of Molecular Modeling·Andreas Lynge VishartKurt V Mikkelsen
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Aug 28, 2021·Nanomaterials·Elie GeageaFrédéric Chérioux
Oct 30, 2021·The Journal of Physical Chemistry. C, Nanomaterials and Interfaces·Christophe NacciLeonhard Grill

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Methods Mentioned

BETA
atomic force microscopy

Software Mentioned

CP2K
WSxM

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