The Effect of Glycol Side Chains on the Assembly and Microstructure of Conjugated Polymers

Stefania Moro; Nicholas Siemons; Oscar Drury; Daniel A. Warr; Thomas A. Moriarty; Luís M.A. Perdigão; Drew Pearce; Maximilian Moser; Rawad K. Hallani; Joseph Parker; Iain McCulloch; Jarvist M. Frost; Jenny Nelson; Giovanni Costantini

doi:10.1021/acsnano.2c09464

The Effect of Glycol Side Chains on the Assembly and Microstructure of Conjugated Polymers

Stefania Moro, Nicholas Siemons, Oscar Drury, Daniel A. Warr, Thomas A. Moriarty, Luís M.A. Perdigão, Drew Pearce, Maximilian Moser, Rawad K. Hallani, Joseph Parker, Iain McCulloch, Jarvist M. Frost, Jenny Nelson, Giovanni Costantini^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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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.

Original language	English
Pages (from-to)	21303-21314
Number of pages	12
Journal	ACS Nano
Volume	16
Issue number	12
Early online date	14 Dec 2022
DOIs	https://doi.org/10.1021/acsnano.2c09464
Publication status	Published - 27 Dec 2022

Bibliographical note

Funding Information:
S.M. acknowledges funding though an EU Chancellor’s Scholarship by the University of Warwick. J.P. acknowledges support by the Biotechnology and Biological Sciences Research Council (BBSRC) and University of Warwick funded Midlands Integrative Biosciences Training Partnership (MIBTP) (grant number BB/M01116X/1). J.N., N.S., and D.P. acknowledge funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement no. 742708, project CAPaCITy). J.N. thanks the Royal Society for award of a Research Professorship. J.M.F. is supported by a Royal Society University Research Fellowship (URF-R1-191292). This research was funded in part, by the European Union’s Horizon 2020 research and innovation program under grant agreement no. 952911, project BOOSTER and grant agreement no. 862474, project RoLA-FLEX, as well as the Engineering and Physical Sciences Research Council (EPSRC) under project EP/T026219/1. This work was in part funded by UKRI grants. For the purpose of open access, the author has applied a Creative Commons Attribution (CC BY) licence to any Author Accepted Manuscript version arising.

Keywords

conjugated polymers
glycolated side chains
microstructure
molecular dynamics
scanning tunneling microscopy

ASJC Scopus subject areas

General Materials Science
General Engineering
General Physics and Astronomy

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10.1021/acsnano.2c09464Licence: Creative Commons: Attribution (CC BY)

MoroSS2022EffeectFinal published version, 2.9 MBLicence: Creative Commons: Attribution (CC BY)

Cite this

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title = "The Effect of Glycol Side Chains on the Assembly and Microstructure of Conjugated Polymers",

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.",

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author = "Stefania Moro and Nicholas Siemons and Oscar Drury and Warr, {Daniel A.} and Moriarty, {Thomas A.} and Perdig{\~a}o, {Lu{\'i}s M.A.} and Drew Pearce and Maximilian Moser and Hallani, {Rawad K.} and Joseph Parker and Iain McCulloch and Frost, {Jarvist M.} and Jenny Nelson and Giovanni Costantini",

note = "Funding Information: S.M. acknowledges funding though an EU Chancellor{\textquoteright}s Scholarship by the University of Warwick. J.P. acknowledges support by the Biotechnology and Biological Sciences Research Council (BBSRC) and University of Warwick funded Midlands Integrative Biosciences Training Partnership (MIBTP) (grant number BB/M01116X/1). J.N., N.S., and D.P. acknowledge funding from the European Research Council (ERC) under the European Union{\textquoteright}s Horizon 2020 research and innovation program (grant agreement no. 742708, project CAPaCITy). J.N. thanks the Royal Society for award of a Research Professorship. J.M.F. is supported by a Royal Society University Research Fellowship (URF-R1-191292). This research was funded in part, by the European Union{\textquoteright}s Horizon 2020 research and innovation program under grant agreement no. 952911, project BOOSTER and grant agreement no. 862474, project RoLA-FLEX, as well as the Engineering and Physical Sciences Research Council (EPSRC) under project EP/T026219/1. This work was in part funded by UKRI grants. For the purpose of open access, the author has applied a Creative Commons Attribution (CC BY) licence to any Author Accepted Manuscript version arising.",

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AU - Siemons, Nicholas

AU - Drury, Oscar

AU - Warr, Daniel A.

AU - Moriarty, Thomas A.

AU - Perdigão, Luís M.A.

AU - Pearce, Drew

AU - Moser, Maximilian

AU - Hallani, Rawad K.

AU - Parker, Joseph

AU - McCulloch, Iain

AU - Frost, Jarvist M.

AU - Nelson, Jenny

AU - Costantini, Giovanni

N1 - Funding Information: S.M. acknowledges funding though an EU Chancellor’s Scholarship by the University of Warwick. J.P. acknowledges support by the Biotechnology and Biological Sciences Research Council (BBSRC) and University of Warwick funded Midlands Integrative Biosciences Training Partnership (MIBTP) (grant number BB/M01116X/1). J.N., N.S., and D.P. acknowledge funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (grant agreement no. 742708, project CAPaCITy). J.N. thanks the Royal Society for award of a Research Professorship. J.M.F. is supported by a Royal Society University Research Fellowship (URF-R1-191292). This research was funded in part, by the European Union’s Horizon 2020 research and innovation program under grant agreement no. 952911, project BOOSTER and grant agreement no. 862474, project RoLA-FLEX, as well as the Engineering and Physical Sciences Research Council (EPSRC) under project EP/T026219/1. This work was in part funded by UKRI grants. For the purpose of open access, the author has applied a Creative Commons Attribution (CC BY) licence to any Author Accepted Manuscript version arising.

PY - 2022/12/27

Y1 - 2022/12/27

N2 - 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.

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The Effect of Glycol Side Chains on the Assembly and Microstructure of Conjugated Polymers

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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