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The effect of glycol side chains on the assembly and microstructure of conjugated polymers
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Moro, Stefania, Siemons, Nicholas, Drury, Oscar, Warr, Daniel A., Moriarty, Thomas A., Perdigão, Luís M. A., Pearce, Drew, Moser, Maximilian, Hallani, Rawad K., Parker, Joseph, McCulloch, Iain, Frost, Jarvist M., Nelson, Jenny and Costantini, Giovanni (2022) The effect of glycol side chains on the assembly and microstructure of conjugated polymers. ACS Nano, 16 (12). pp. 21303-21314. doi:10.1021/acsnano.2c09464 ISSN 1936-0851.
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Official URL: http://doi.org/10.1021/acsnano.2c09464
Abstract
Conjugated polymers with glycol-based chains, are emerging as a material class with promising applications as organic mixed ionic-electronic conductors, particularly in bioelectronics and thermoelectrics. However, little is still known about their microstructure and the role of the side chains in determining intermolecular interactions and polymer packing. Here, we use the combination of electrospray deposition and scanning tunneling microscopy to determine the microstructure of prototypical glycolated conjugated polymers (pgBTTT and p(g2T-TT)) with submonomer resolution. Molecular dynamics simulations of the same surface-adsorbed polymers exhibit an excellent agreement with the experimental images, allowing us to extend the characterization of the polymers to the atomic scale. Our results prove that, similarly to their alkylated counterparts, glycolated polymers assemble through interdigitation of their side chains, although significant differences are found in their conformation and interaction patterns. A model is proposed that identifies the driving force for the polymer assembly in the tendency of the side chains to adopt the conformation of their free analogues, i.e., polyethylene and polyethylene glycol, for alkyl or ethylene glycol side chains, respectively. For both classes of polymers, it is also demonstrated that the backbone conformation is determined to a higher degree by the interaction between the side chains rather than by the backbone torsional potential energy. The generalization of these findings from two-dimensional (2D) monolayers to three-dimensional thin films is discussed, together with the opportunity to use this type of 2D study to gain so far inaccessible, subnm-scale information on the microstructure of conjugated polymers.
| Item Type: | Journal Article | ||||||||
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||
| Journal or Publication Title: | ACS Nano | ||||||||
| Publisher: | American Chemical Society | ||||||||
| ISSN: | 1936-0851 | ||||||||
| Official Date: | 27 December 2022 | ||||||||
| Dates: |
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| Volume: | 16 | ||||||||
| Number: | 12 | ||||||||
| Page Range: | pp. 21303-21314 | ||||||||
| DOI: | 10.1021/acsnano.2c09464 | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Access rights to Published version: | Open Access (Creative Commons) | ||||||||
| Copyright Holders: | Copyright © 2022 The Authors. Published by American Chemical Society | ||||||||
| Date of first compliant deposit: | 8 February 2023 | ||||||||
| Date of first compliant Open Access: | 8 February 2023 |
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