New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations
Autor(a) principal: | |
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Data de Publicação: | 2021 |
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/10316/105263 https://doi.org/10.3390/molecules26102934 |
Resumo: | A set of 3-ethynylaryl coumarin dyes with mono, bithiophenes and the fused variant, thieno [3,2-b] thiophene, as well as an alkylated benzotriazole unit were prepared and tested for dye-sensitized solar cells (DSSCs). For comparison purposes, the variation of the substitution pattern at the coumarin unit was analyzed with the natural product 6,7-dihydroxycoumarin (Esculetin) as well as 5,7-dihydroxycomarin in the case of the bithiophene dye. Crucial steps for extension of the conjugated system involved Sonogashira reaction yielding highly fluorescent molecules. Spectroscopic characterization showed that the extension of conjugation via the alkynyl bridge resulted in a strong red-shift of absorption and emission spectra (in solution) of approximately 73-79 nm and 52-89 nm, respectively, relative to 6,7-dimethoxy-4-methylcoumarin (λabs = 341 nm and λem = 410 nm). Theoretical density functional theory (DFT) calculations show that the Lowest Unoccupied Molecular Orbital (LUMO) is mostly centered in the cyanoacrylic anchor unit, corroborating the high intramolecular charge transfer (ICT) character of the electronic transition. Photovoltaic performance evaluation reveals that the thieno [3,2-b] thiophene unit present in dye 8 leads to the best sensitizer of the set, with a conversion efficiency (η = 2.00%), best VOC (367 mV) and second best Jsc (9.28 mA·cm-2), surpassed only by dye 9b (Jsc = 10.19 mA·cm-2). This high photocurrent value can be attributed to increased donor ability of the 5,7-dimethoxy unit when compared to the 6,7 equivalent (9b). |
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New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculationsdye-sensitized solar cellscoumarin dyesthieno [3,2-b] thiophenecharge transferethynylarylA set of 3-ethynylaryl coumarin dyes with mono, bithiophenes and the fused variant, thieno [3,2-b] thiophene, as well as an alkylated benzotriazole unit were prepared and tested for dye-sensitized solar cells (DSSCs). For comparison purposes, the variation of the substitution pattern at the coumarin unit was analyzed with the natural product 6,7-dihydroxycoumarin (Esculetin) as well as 5,7-dihydroxycomarin in the case of the bithiophene dye. Crucial steps for extension of the conjugated system involved Sonogashira reaction yielding highly fluorescent molecules. Spectroscopic characterization showed that the extension of conjugation via the alkynyl bridge resulted in a strong red-shift of absorption and emission spectra (in solution) of approximately 73-79 nm and 52-89 nm, respectively, relative to 6,7-dimethoxy-4-methylcoumarin (λabs = 341 nm and λem = 410 nm). Theoretical density functional theory (DFT) calculations show that the Lowest Unoccupied Molecular Orbital (LUMO) is mostly centered in the cyanoacrylic anchor unit, corroborating the high intramolecular charge transfer (ICT) character of the electronic transition. Photovoltaic performance evaluation reveals that the thieno [3,2-b] thiophene unit present in dye 8 leads to the best sensitizer of the set, with a conversion efficiency (η = 2.00%), best VOC (367 mV) and second best Jsc (9.28 mA·cm-2), surpassed only by dye 9b (Jsc = 10.19 mA·cm-2). This high photocurrent value can be attributed to increased donor ability of the 5,7-dimethoxy unit when compared to the 6,7 equivalent (9b).MDPI2021-05-14info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/105263http://hdl.handle.net/10316/105263https://doi.org/10.3390/molecules26102934eng1420-3049Sarrato, JoãoPinto, Ana LuciaMalta, GabrielaRöck, Eva GPina, JoãoLima, João CarlosParola, A. JorgeBranco, Paula Sérioinfo: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:RCAAP2023-02-13T11:26:13Zoai:estudogeral.uc.pt:10316/105263Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:21:51.675384Repositório 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 |
New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations |
title |
New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations |
spellingShingle |
New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations Sarrato, João dye-sensitized solar cells coumarin dyes thieno [3,2-b] thiophene charge transfer ethynylaryl |
title_short |
New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations |
title_full |
New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations |
title_fullStr |
New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations |
title_full_unstemmed |
New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations |
title_sort |
New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations |
author |
Sarrato, João |
author_facet |
Sarrato, João Pinto, Ana Lucia Malta, Gabriela Röck, Eva G Pina, João Lima, João Carlos Parola, A. Jorge Branco, Paula Sério |
author_role |
author |
author2 |
Pinto, Ana Lucia Malta, Gabriela Röck, Eva G Pina, João Lima, João Carlos Parola, A. Jorge Branco, Paula Sério |
author2_role |
author author author author author author author |
dc.contributor.author.fl_str_mv |
Sarrato, João Pinto, Ana Lucia Malta, Gabriela Röck, Eva G Pina, João Lima, João Carlos Parola, A. Jorge Branco, Paula Sério |
dc.subject.por.fl_str_mv |
dye-sensitized solar cells coumarin dyes thieno [3,2-b] thiophene charge transfer ethynylaryl |
topic |
dye-sensitized solar cells coumarin dyes thieno [3,2-b] thiophene charge transfer ethynylaryl |
description |
A set of 3-ethynylaryl coumarin dyes with mono, bithiophenes and the fused variant, thieno [3,2-b] thiophene, as well as an alkylated benzotriazole unit were prepared and tested for dye-sensitized solar cells (DSSCs). For comparison purposes, the variation of the substitution pattern at the coumarin unit was analyzed with the natural product 6,7-dihydroxycoumarin (Esculetin) as well as 5,7-dihydroxycomarin in the case of the bithiophene dye. Crucial steps for extension of the conjugated system involved Sonogashira reaction yielding highly fluorescent molecules. Spectroscopic characterization showed that the extension of conjugation via the alkynyl bridge resulted in a strong red-shift of absorption and emission spectra (in solution) of approximately 73-79 nm and 52-89 nm, respectively, relative to 6,7-dimethoxy-4-methylcoumarin (λabs = 341 nm and λem = 410 nm). Theoretical density functional theory (DFT) calculations show that the Lowest Unoccupied Molecular Orbital (LUMO) is mostly centered in the cyanoacrylic anchor unit, corroborating the high intramolecular charge transfer (ICT) character of the electronic transition. Photovoltaic performance evaluation reveals that the thieno [3,2-b] thiophene unit present in dye 8 leads to the best sensitizer of the set, with a conversion efficiency (η = 2.00%), best VOC (367 mV) and second best Jsc (9.28 mA·cm-2), surpassed only by dye 9b (Jsc = 10.19 mA·cm-2). This high photocurrent value can be attributed to increased donor ability of the 5,7-dimethoxy unit when compared to the 6,7 equivalent (9b). |
publishDate |
2021 |
dc.date.none.fl_str_mv |
2021-05-14 |
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/10316/105263 http://hdl.handle.net/10316/105263 https://doi.org/10.3390/molecules26102934 |
url |
http://hdl.handle.net/10316/105263 https://doi.org/10.3390/molecules26102934 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
1420-3049 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
MDPI |
publisher.none.fl_str_mv |
MDPI |
dc.source.none.fl_str_mv |
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 |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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