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 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 Hallani, Joseph Parker, Iain McCulloch, Jarvist M. Frost, Jenny Nelson, Giovanni Costantini

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

33 Scopus citations

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 (US)
Journal	ACS Nano
DOIs	https://doi.org/10.1021/acsnano.2c09464
State	Published - Dec 14 2022

Bibliographical note

KAUST Repository Item: Exported on 2022-12-19
Acknowledgements: 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.

ASJC Scopus subject areas

General Physics and Astronomy
General Materials Science
General Engineering

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https://repository.kaust.edu.sa/bitstream/10754/686509/1/acsnano.2c09464.pdf

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@article{8c259371c779405bb89b37948a0769c0,

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.",

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 Rawad Hallani and Joseph Parker and Iain McCulloch and Frost, {Jarvist M.} and Jenny Nelson and Giovanni Costantini",

note = "KAUST Repository Item: Exported on 2022-12-19 Acknowledgements: 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.",

year = "2022",

month = dec,

day = "14",

doi = "10.1021/acsnano.2c09464",

language = "English (US)",

journal = "ACS Nano",

issn = "1936-0851",

publisher = "American Chemical Society",

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TY - JOUR

T1 - The Effect of Glycol Side Chains on the Assembly and Microstructure of Conjugated Polymers

AU - Moro, Stefania

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

AU - Parker, Joseph

AU - McCulloch, Iain

AU - Frost, Jarvist M.

AU - Nelson, Jenny

AU - Costantini, Giovanni

N1 - KAUST Repository Item: Exported on 2022-12-19 Acknowledgements: 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.

PY - 2022/12/14

Y1 - 2022/12/14

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.

AB - 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.

UR - http://hdl.handle.net/10754/686509

UR - https://pubs.acs.org/doi/10.1021/acsnano.2c09464

U2 - 10.1021/acsnano.2c09464

DO - 10.1021/acsnano.2c09464

M3 - Article

C2 - 36516000

SN - 1936-0851

JO - ACS Nano

JF - ACS Nano

ER -

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

Abstract

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