Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives

One factor with great bearing on the electrochemical performance of conjugated polymers is the film morphology. A balance between crystalline and amorphous domains needs to be achieved for the polymer to have an optimal ionic-electronic conductance. Herein, the morphological and electrochemical prop...

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Autores: Hopkins, Jonathan, Ta, Daniel, Lauto, Antonio, Baker, Carly, Daniels, John, Wagner, Pawel, Wagner, Klaudia, Kirby, Nigel, Cazorla Silva, Claudio|||0000-0002-6501-4513, Officer, David, Mawad, Damia
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universitat Politècnica de Catalunya (UPC)
Repositorio:UPCommons. Portal del coneixement obert de la UPC
Idioma:inglés
OAI Identifier:oai:upcommons.upc.edu:2117/403219
Acceso en línea:https://hdl.handle.net/2117/403219
https://dx.doi.org/10.1002/admt.202300777
Access Level:acceso abierto
Palabra clave:Phosphonates
Electrochemistry
Paracrystalline
Phosphonate
Poly(ethylenedioxythiophene)
Electroquímica
Fosfonats
Àrees temàtiques de la UPC::Física
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spelling Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivativesHopkins, JonathanTa, DanielLauto, AntonioBaker, CarlyDaniels, JohnWagner, PawelWagner, KlaudiaKirby, NigelCazorla Silva, Claudio|||0000-0002-6501-4513Officer, DavidMawad, DamiaPhosphonatesElectrochemistryParacrystallinePhosphonatePoly(ethylenedioxythiophene)ElectroquímicaFosfonatsÀrees temàtiques de la UPC::FísicaOne factor with great bearing on the electrochemical performance of conjugated polymers is the film morphology. A balance between crystalline and amorphous domains needs to be achieved for the polymer to have an optimal ionic-electronic conductance. Herein, the morphological and electrochemical properties of poly(ethylenedioxythiophene) polymers functionalized with phosphonate groups separated by methylene and butylene alkyl spacers from the backbone are compared. Extending the spacer from methylene to butylene increases structural ordering in the solid state as revealed by grazing-incidence wide-angle X-ray scattering. However, the ordered domains are only short range, suggestive of a paracrystalline morphology in which ordered regions are separated by amorphous regions. This has a negative impact on the intermolecular charge transport. The longer spacer appears to have impeded the uptake of hydrated counterions, seen by the increase in the ionization potential and energy requirement for electrochemical switching, as well as the decrease in the volumetric capacitance. These results elucidate the advantages of having the phosphonate pendant group close to the backbone, separated only by a methylene spacer. This synthetic design likely facilitates hydrated counterions to accumulate around the polar phosphonate groups, close to the doped backbone where they can easily compensate the charge carriers formed upon oxidation.A.L., D.L.O., and D.M. would like to acknowledge the Australian Research Council, Discovery Project Grant DP190102560, for funding this research. The authors would like to acknowledge the use of facilities and the assistance of Dr. David Miskovic of the UNSW School of Materials Science and Engineering, Dr. Anne Rich of the Spectroscopy Laboratory, Dr. Bill Bin Gong and Dr. Yu Wang in the Solid State & Elemental Analysis Unit, as well as the members of the NMR Facility under the Mark Wainwright Analytical Centre at UNSW Sydney.Peer Reviewed20232023-06-2720242024-02-26journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/2117/403219https://dx.doi.org/10.1002/admt.202300777reponame:UPCommons. Portal del coneixement obert de la UPCinstname:Universitat Politècnica de Catalunya (UPC)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:upcommons.upc.edu:2117/4032192026-05-27T15:37:01Z
dc.title.none.fl_str_mv Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives
title Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives
spellingShingle Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives
Hopkins, Jonathan
Phosphonates
Electrochemistry
Paracrystalline
Phosphonate
Poly(ethylenedioxythiophene)
Electroquímica
Fosfonats
Àrees temàtiques de la UPC::Física
title_short Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives
title_full Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives
title_fullStr Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives
title_full_unstemmed Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives
title_sort Impact of side chain extension on the morphology and electrochemistry of phosphonated poly(ethylenedioxythiophene) derivatives
dc.creator.none.fl_str_mv Hopkins, Jonathan
Ta, Daniel
Lauto, Antonio
Baker, Carly
Daniels, John
Wagner, Pawel
Wagner, Klaudia
Kirby, Nigel
Cazorla Silva, Claudio|||0000-0002-6501-4513
Officer, David
Mawad, Damia
author Hopkins, Jonathan
author_facet Hopkins, Jonathan
Ta, Daniel
Lauto, Antonio
Baker, Carly
Daniels, John
Wagner, Pawel
Wagner, Klaudia
Kirby, Nigel
Cazorla Silva, Claudio|||0000-0002-6501-4513
Officer, David
Mawad, Damia
author_role author
author2 Ta, Daniel
Lauto, Antonio
Baker, Carly
Daniels, John
Wagner, Pawel
Wagner, Klaudia
Kirby, Nigel
Cazorla Silva, Claudio|||0000-0002-6501-4513
Officer, David
Mawad, Damia
author2_role author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Phosphonates
Electrochemistry
Paracrystalline
Phosphonate
Poly(ethylenedioxythiophene)
Electroquímica
Fosfonats
Àrees temàtiques de la UPC::Física
topic Phosphonates
Electrochemistry
Paracrystalline
Phosphonate
Poly(ethylenedioxythiophene)
Electroquímica
Fosfonats
Àrees temàtiques de la UPC::Física
description One factor with great bearing on the electrochemical performance of conjugated polymers is the film morphology. A balance between crystalline and amorphous domains needs to be achieved for the polymer to have an optimal ionic-electronic conductance. Herein, the morphological and electrochemical properties of poly(ethylenedioxythiophene) polymers functionalized with phosphonate groups separated by methylene and butylene alkyl spacers from the backbone are compared. Extending the spacer from methylene to butylene increases structural ordering in the solid state as revealed by grazing-incidence wide-angle X-ray scattering. However, the ordered domains are only short range, suggestive of a paracrystalline morphology in which ordered regions are separated by amorphous regions. This has a negative impact on the intermolecular charge transport. The longer spacer appears to have impeded the uptake of hydrated counterions, seen by the increase in the ionization potential and energy requirement for electrochemical switching, as well as the decrease in the volumetric capacitance. These results elucidate the advantages of having the phosphonate pendant group close to the backbone, separated only by a methylene spacer. This synthetic design likely facilitates hydrated counterions to accumulate around the polar phosphonate groups, close to the doped backbone where they can easily compensate the charge carriers formed upon oxidation.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023-06-27
2024
2024-02-26
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/2117/403219
https://dx.doi.org/10.1002/admt.202300777
url https://hdl.handle.net/2117/403219
https://dx.doi.org/10.1002/admt.202300777
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:UPCommons. Portal del coneixement obert de la UPC
instname:Universitat Politècnica de Catalunya (UPC)
instname_str Universitat Politècnica de Catalunya (UPC)
reponame_str UPCommons. Portal del coneixement obert de la UPC
collection UPCommons. Portal del coneixement obert de la UPC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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