New 3-Ethynylaryl Coumarin-Based Dyes for DSSC Applications: Synthesis, Spectroscopic Properties, and Theoretical Calculations

Detalhes bibliográficos
Autor(a) principal: Sarrato, João
Data de Publicação: 2021
Outros Autores: Pinto, Ana Lucia, Malta, Gabriela, Röck, Eva G, Pina, João, Lima, João Carlos, Parola, A. Jorge, Branco, Paula Sério
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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spelling 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
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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
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dc.relation.none.fl_str_mv 1420-3049
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
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dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
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