Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes
Autor(a) principal: | |
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Data de Publicação: | 2020 |
Outros Autores: | , , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10316/90799 https://doi.org/10.1021/acs.jpcc.9b10908 |
Resumo: | Two new polythiophenes functionalized with different degrees of tetraphenylethene, TPE, side groups (with TPE moieties at each thiophene unit, homoPT, and one in which only each second thiophene unit carries a TPE side chain, coPT) were successfully synthesized and characterized together with a poly(3-hexylthiophene) with similar average molecular weight and a tetraphenylethene-thiophene model compound. The study aimed to understand the role of the sterically bulky TPE pendant groups on the inhibition of intra- and/or interchain packing (aggregation) of these conjugated polymers. For the tetraphenylethenethiophene model, compound aggregation induced emission (AIE) is active for water fractions ≥ 90%. An opposite behavior is found for the polythiophenes (homoPT and coPT) where aggregation caused quenching (ACQ) was found to occur both in solution and in the solid state. For the polythiophene with the higher degree of TPE labeling, homoPT, the amount of ACQ is significantly decreased. This is attributed to the high TPE substitution density in the polymer which promotes a more twisted conformation of the polymer backbone as the emissive chromophore. For the TPE-polythiophenes, only the energy migration mechanism was found to be active since the bulky TPE substituents restrict the polymer’s intramolecular motions. The experimental observations of a small shift in the emission spectra of homoPT and significant hindering of ACQ on going from solution to the solid state explain the absence of intermolecular interactions together with the restriction of intramolecular rotations. |
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Restricted Aggregate Formation on Tetraphenylethene-Substituted PolythiophenesTwo new polythiophenes functionalized with different degrees of tetraphenylethene, TPE, side groups (with TPE moieties at each thiophene unit, homoPT, and one in which only each second thiophene unit carries a TPE side chain, coPT) were successfully synthesized and characterized together with a poly(3-hexylthiophene) with similar average molecular weight and a tetraphenylethene-thiophene model compound. The study aimed to understand the role of the sterically bulky TPE pendant groups on the inhibition of intra- and/or interchain packing (aggregation) of these conjugated polymers. For the tetraphenylethenethiophene model, compound aggregation induced emission (AIE) is active for water fractions ≥ 90%. An opposite behavior is found for the polythiophenes (homoPT and coPT) where aggregation caused quenching (ACQ) was found to occur both in solution and in the solid state. For the polythiophene with the higher degree of TPE labeling, homoPT, the amount of ACQ is significantly decreased. This is attributed to the high TPE substitution density in the polymer which promotes a more twisted conformation of the polymer backbone as the emissive chromophore. For the TPE-polythiophenes, only the energy migration mechanism was found to be active since the bulky TPE substituents restrict the polymer’s intramolecular motions. The experimental observations of a small shift in the emission spectra of homoPT and significant hindering of ACQ on going from solution to the solid state explain the absence of intermolecular interactions together with the restriction of intramolecular rotations.ACS Publications2020info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/90799http://hdl.handle.net/10316/90799https://doi.org/10.1021/acs.jpcc.9b10908eng1932-74471932-7455https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.9b10908Pina, JoãoRodrigues, Ana Clara B.Alnady, Mohamed Maged Saad AbdelatiDong, WenyueScherf, UllrichMelo, J. Sérgio Seixas deinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2022-05-25T06:22:25Zoai:estudogeral.uc.pt:10316/90799Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:10:49.600039Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes |
title |
Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes |
spellingShingle |
Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes Pina, João |
title_short |
Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes |
title_full |
Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes |
title_fullStr |
Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes |
title_full_unstemmed |
Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes |
title_sort |
Restricted Aggregate Formation on Tetraphenylethene-Substituted Polythiophenes |
author |
Pina, João |
author_facet |
Pina, João Rodrigues, Ana Clara B. Alnady, Mohamed Maged Saad Abdelati Dong, Wenyue Scherf, Ullrich Melo, J. Sérgio Seixas de |
author_role |
author |
author2 |
Rodrigues, Ana Clara B. Alnady, Mohamed Maged Saad Abdelati Dong, Wenyue Scherf, Ullrich Melo, J. Sérgio Seixas de |
author2_role |
author author author author author |
dc.contributor.author.fl_str_mv |
Pina, João Rodrigues, Ana Clara B. Alnady, Mohamed Maged Saad Abdelati Dong, Wenyue Scherf, Ullrich Melo, J. Sérgio Seixas de |
description |
Two new polythiophenes functionalized with different degrees of tetraphenylethene, TPE, side groups (with TPE moieties at each thiophene unit, homoPT, and one in which only each second thiophene unit carries a TPE side chain, coPT) were successfully synthesized and characterized together with a poly(3-hexylthiophene) with similar average molecular weight and a tetraphenylethene-thiophene model compound. The study aimed to understand the role of the sterically bulky TPE pendant groups on the inhibition of intra- and/or interchain packing (aggregation) of these conjugated polymers. For the tetraphenylethenethiophene model, compound aggregation induced emission (AIE) is active for water fractions ≥ 90%. An opposite behavior is found for the polythiophenes (homoPT and coPT) where aggregation caused quenching (ACQ) was found to occur both in solution and in the solid state. For the polythiophene with the higher degree of TPE labeling, homoPT, the amount of ACQ is significantly decreased. This is attributed to the high TPE substitution density in the polymer which promotes a more twisted conformation of the polymer backbone as the emissive chromophore. For the TPE-polythiophenes, only the energy migration mechanism was found to be active since the bulky TPE substituents restrict the polymer’s intramolecular motions. The experimental observations of a small shift in the emission spectra of homoPT and significant hindering of ACQ on going from solution to the solid state explain the absence of intermolecular interactions together with the restriction of intramolecular rotations. |
publishDate |
2020 |
dc.date.none.fl_str_mv |
2020 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10316/90799 http://hdl.handle.net/10316/90799 https://doi.org/10.1021/acs.jpcc.9b10908 |
url |
http://hdl.handle.net/10316/90799 https://doi.org/10.1021/acs.jpcc.9b10908 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
1932-7447 1932-7455 https://pubs.acs.org/doi/abs/10.1021/acs.jpcc.9b10908 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
ACS Publications |
publisher.none.fl_str_mv |
ACS Publications |
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reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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RCAAP |
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RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799134004146864128 |