Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers
Glycol sidechains are often used to enhance the performance of organic photoconversion and electrochemical devices. Herein, we study their effects on electronic states and electronic properties. We find that polymer glycolation not only induces more disordered packing, but also results in a higher r...
| Autores: | , , , , , , , , , , , , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/365380 |
| Acceso en línea: | http://hdl.handle.net/10261/365380 https://api.elsevier.com/content/abstract/scopus_id/85199133537 |
| Access Level: | acceso abierto |
| Palabra clave: | Side chains Replacing alkyl Charge transfer Oligothiophenes Fluorescence Spectroscopy |
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| dc.title.none.fl_str_mv |
Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers |
| title |
Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers |
| spellingShingle |
Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers Pagano, Katia Side chains Replacing alkyl Charge transfer Oligothiophenes Fluorescence Spectroscopy |
| title_short |
Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers |
| title_full |
Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers |
| title_fullStr |
Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers |
| title_full_unstemmed |
Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers |
| title_sort |
Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymers |
| dc.creator.none.fl_str_mv |
Pagano, Katia Kim, Jin Gwan Luke, Joel Tan, Ellasia Stewart, Katherine Sazanovich, Igor V. Karras, Gabriel Gonev, Hristo Ivov Marsh, Adam V. Kim, Na Yeong Kwon, Sooncheol Kim, Young Yong Alonso Carmona, M. Isabel Dörling, Bernhard Campoy Quiles, Mariano Parker, Anthony W. Clarke, Tracey M. Kim, Yun-Hi Kim, Ji-Seon |
| author |
Pagano, Katia |
| author_facet |
Pagano, Katia Kim, Jin Gwan Luke, Joel Tan, Ellasia Stewart, Katherine Sazanovich, Igor V. Karras, Gabriel Gonev, Hristo Ivov Marsh, Adam V. Kim, Na Yeong Kwon, Sooncheol Kim, Young Yong Alonso Carmona, M. Isabel Dörling, Bernhard Campoy Quiles, Mariano Parker, Anthony W. Clarke, Tracey M. Kim, Yun-Hi Kim, Ji-Seon |
| author_role |
author |
| author2 |
Kim, Jin Gwan Luke, Joel Tan, Ellasia Stewart, Katherine Sazanovich, Igor V. Karras, Gabriel Gonev, Hristo Ivov Marsh, Adam V. Kim, Na Yeong Kwon, Sooncheol Kim, Young Yong Alonso Carmona, M. Isabel Dörling, Bernhard Campoy Quiles, Mariano Parker, Anthony W. Clarke, Tracey M. Kim, Yun-Hi Kim, Ji-Seon |
| author2_role |
author author author author author author author author author author author author author author author author author author |
| dc.contributor.none.fl_str_mv |
Department for Business, Energy and Industrial Strategy (UK) Engineering and Physical Sciences Research Council (UK) National Research Foundation of Korea Ministerio de Ciencia, Innovación y Universidades (España) Ministerio de Ciencia e Innovación (España) Agencia Estatal de Investigación (España) Generalitat de Catalunya Pagano, Katia [0000-0002-7680-9370] Luke, Joel [0000-0003-3208-8572] Sazanovich, Igor V. [0000-0002-8000-7645] Gonev, Hristo Ivov [0000-0002-9752-4008] Kim, Young Yong [0000-0001-6102-9518] Alonso Carmona, M. Isabel [0000-0001-7669-5871] Dörling, Bernhard [0000-0003-3171-0526] Campoy Quiles, Mariano [0000-0002-8911-640X] Parker, Anthony W. [0000-0003-3094-9762] Clarke, Tracey M. [0000-0003-4943-0645] Kim, Yun-Hi [0000-0001-8856-4414] Kim, Ji-Seon [0000-0003-4715-3656] Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72] |
| dc.subject.none.fl_str_mv |
Side chains Replacing alkyl Charge transfer Oligothiophenes Fluorescence Spectroscopy |
| topic |
Side chains Replacing alkyl Charge transfer Oligothiophenes Fluorescence Spectroscopy |
| description |
Glycol sidechains are often used to enhance the performance of organic photoconversion and electrochemical devices. Herein, we study their effects on electronic states and electronic properties. We find that polymer glycolation not only induces more disordered packing, but also results in a higher reorganisation energy due to more localised π-electron density. Transient absorption spectroscopy and femtosecond stimulated Raman spectroscopy are utilised to monitor the structural relaxation dynamics coupled to the excited state formation upon photoexcitation. Singlet excitons are initially formed, followed by polaron pair formation. The associated structural relaxation slows down in glycolated polymers (5 ps vs. 1.25 ps for alkylated), consistent with larger reorganisation energy. This slower vibrational relaxation is found to drive ultrafast formation of the polaron pair state (5 ps vs. 10 ps for alkylated). These results provide key experimental evidence demonstrating the impact of molecular structure on electronic state formation driven by strong vibrational coupling. |
| publishDate |
2024 |
| dc.date.none.fl_str_mv |
2024 2024 2024 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/article http://purl.org/coar/resource_type/c_6501 Publisher's version info:eu-repo/semantics/publishedVersion |
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article |
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publishedVersion |
| dc.identifier.none.fl_str_mv |
http://hdl.handle.net/10261/365380 https://api.elsevier.com/content/abstract/scopus_id/85199133537 |
| url |
http://hdl.handle.net/10261/365380 https://api.elsevier.com/content/abstract/scopus_id/85199133537 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.relation.none.fl_str_mv |
#PLACEHOLDER_PARENT_METADATA_VALUE# #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-128924OB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/CEX2019-000917-S Nature communications http://doi.org/10.1038/s41467-024-50530-7 Sí |
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info:eu-repo/semantics/openAccess |
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openAccess |
| dc.publisher.none.fl_str_mv |
Nature Publishing Group |
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Nature Publishing Group |
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reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC instname:Consejo Superior de Investigaciones Científicas (CSIC) |
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Consejo Superior de Investigaciones Científicas (CSIC) |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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DIGITAL.CSIC. Repositorio Institucional del CSIC |
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1869419521485307904 |
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Slow vibrational relaxation drives ultrafast formation of photoexcited polaron pair states in glycolated conjugated polymersPagano, KatiaKim, Jin GwanLuke, JoelTan, EllasiaStewart, KatherineSazanovich, Igor V.Karras, GabrielGonev, Hristo IvovMarsh, Adam V.Kim, Na YeongKwon, SooncheolKim, Young YongAlonso Carmona, M. IsabelDörling, BernhardCampoy Quiles, MarianoParker, Anthony W.Clarke, Tracey M.Kim, Yun-HiKim, Ji-SeonSide chainsReplacing alkylCharge transferOligothiophenesFluorescenceSpectroscopyGlycol sidechains are often used to enhance the performance of organic photoconversion and electrochemical devices. Herein, we study their effects on electronic states and electronic properties. We find that polymer glycolation not only induces more disordered packing, but also results in a higher reorganisation energy due to more localised π-electron density. Transient absorption spectroscopy and femtosecond stimulated Raman spectroscopy are utilised to monitor the structural relaxation dynamics coupled to the excited state formation upon photoexcitation. Singlet excitons are initially formed, followed by polaron pair formation. The associated structural relaxation slows down in glycolated polymers (5 ps vs. 1.25 ps for alkylated), consistent with larger reorganisation energy. This slower vibrational relaxation is found to drive ultrafast formation of the polaron pair state (5 ps vs. 10 ps for alkylated). These results provide key experimental evidence demonstrating the impact of molecular structure on electronic state formation driven by strong vibrational coupling.The authors are thankful for the opportunity and funding made available by the STFC and UKRI for access to the Central Laser Facility (App. #22130036) and would like to acknowledge all CLF staff who aided us with our measurements during our beamtime. The authors would like to thank Prof. James Durrant for insightful discussions and Dr. Sam Hillman for TAS analysis guidance. K.P., J.L., E.T., K.S., and J.S.K. acknowledge the UK EPSRC for studentships under DTG and the Processable Electronics Centre for Doctoral Training (EP/L016702/1). This research was also supported by the UK Department for Business, Energy and Industrial Strategy (BEIS) through the National Measurement System and the Val O’Donoghue PhD Scholarship at Imperial College London. J.L. and J.S.K acknowledge funding from the UK EPSRC ATIP Programme Grant (EP/T028513/1). Y.H.K., J.K. and N.Y.K. acknowledge National Research Foundation grant NRF (RS-2023-00301974) and NRF (RS-2024-00336766) for financial support. T.M.C. and H.I.G. would like to acknowledge support from the EPSRC (EP/N509577/1, EP/T517793/1). B.D., M.I.A. and M.C.Q. thank the financial support from the Spanish Ministry of Science and Innovation through projects PID2021-128924OB-I00 and CEX2019-000917-S (FUNFUTURE, Spanish Severo Ochoa Centre of Excellence program) and Generalitat de Catalunya (2021-SGR-00444).With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S).Peer reviewedNature Publishing GroupDepartment for Business, Energy and Industrial Strategy (UK)Engineering and Physical Sciences Research Council (UK)National Research Foundation of KoreaMinisterio de Ciencia, Innovación y Universidades (España)Ministerio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)Generalitat de CatalunyaPagano, Katia [0000-0002-7680-9370]Luke, Joel [0000-0003-3208-8572]Sazanovich, Igor V. [0000-0002-8000-7645]Gonev, Hristo Ivov [0000-0002-9752-4008]Kim, Young Yong [0000-0001-6102-9518]Alonso Carmona, M. Isabel [0000-0001-7669-5871]Dörling, Bernhard [0000-0003-3171-0526]Campoy Quiles, Mariano [0000-0002-8911-640X]Parker, Anthony W. [0000-0003-3094-9762]Clarke, Tracey M. [0000-0003-4943-0645]Kim, Yun-Hi [0000-0001-8856-4414]Kim, Ji-Seon [0000-0003-4715-3656]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202420242024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/365380https://api.elsevier.com/content/abstract/scopus_id/85199133537reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-128924OB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de investigación Científica y Técnica y de Innovación 2017-2020/CEX2019-000917-SNature communicationshttp://doi.org/10.1038/s41467-024-50530-7Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3653802026-05-22T06:33:51Z |
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15.812429 |