Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas
Ano de defesa: | 2017 |
---|---|
Autor(a) principal: | |
Orientador(a): | |
Banca de defesa: | , , , |
Tipo de documento: | Tese |
Tipo de acesso: | Acesso aberto |
Idioma: | por |
Instituição de defesa: |
Universidade Federal de Santa Maria
Centro de Ciências Naturais e Exatas |
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
Brasil
|
Palavras-chave em Português: | |
Palavras-chave em Inglês: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/12761 |
Resumo: | This thesis describes, initially, the synthesis and photophysical characterization of new sulfides,sulphoxides and vinyl sulfones based dyes. The compounds in question were obtained in good yields and good diastereoselectivity through Horner-Wadsworth- Emmons (HWE) reactions. The compounds absorb light in the UV/Vis region, with the major transitions occurring between – * orbitals. As for the emission, the PS-1 and PS- 2 vinyl sulphides have their maximum emission bands in the blue region of the spectrum. The oxidation to their respective sulphoxides and sulfones, and the attainment of D– –A structure, causes the emission to undergo a bathochromic shift to the green region of the spectrum. These effects are most pronounced in the triphenylamine derivatives (PSO-1 and PSO2-1) and in polar solvents (positive solvatocromism). With the aid of DFT and TD-DFT calculations, it can be observed that this behaviors are related to the formation of intramolecular charge transfer states (ICT) in the excited state. Subsequently, the design, synthesis and characterization of new vinyl sulphides for possible application in dye-sensitized solar cell (DSSCs) are presented. The compounds were designed to have a D– –A structure, where the sulphides would serve as a bridge between the donor (D) and acceptor (A) blocks. The compounds studied were obtained by the HWE and Knoevenagel condensation, in good yields and good diastereoselectivity. Through preliminary photophysical analysis, it has been observed that the dyes have a wide light absorption range (250–550 nm), in particular the dyes derived from malononitrile PCN-1, PCN-2 and PSCN. In addition to being greatly influenced by the nature of the electron acceptor group. These characteristics are in line with that expected for application in DSSCs and are similar to several sensitizing dyes reported in the literature. |
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2018-03-20T14:12:34Z2018-03-20T14:12:34Z2017http://repositorio.ufsm.br/handle/1/12761This thesis describes, initially, the synthesis and photophysical characterization of new sulfides,sulphoxides and vinyl sulfones based dyes. The compounds in question were obtained in good yields and good diastereoselectivity through Horner-Wadsworth- Emmons (HWE) reactions. The compounds absorb light in the UV/Vis region, with the major transitions occurring between – * orbitals. As for the emission, the PS-1 and PS- 2 vinyl sulphides have their maximum emission bands in the blue region of the spectrum. The oxidation to their respective sulphoxides and sulfones, and the attainment of D– –A structure, causes the emission to undergo a bathochromic shift to the green region of the spectrum. These effects are most pronounced in the triphenylamine derivatives (PSO-1 and PSO2-1) and in polar solvents (positive solvatocromism). With the aid of DFT and TD-DFT calculations, it can be observed that this behaviors are related to the formation of intramolecular charge transfer states (ICT) in the excited state. Subsequently, the design, synthesis and characterization of new vinyl sulphides for possible application in dye-sensitized solar cell (DSSCs) are presented. The compounds were designed to have a D– –A structure, where the sulphides would serve as a bridge between the donor (D) and acceptor (A) blocks. The compounds studied were obtained by the HWE and Knoevenagel condensation, in good yields and good diastereoselectivity. Through preliminary photophysical analysis, it has been observed that the dyes have a wide light absorption range (250–550 nm), in particular the dyes derived from malononitrile PCN-1, PCN-2 and PSCN. In addition to being greatly influenced by the nature of the electron acceptor group. These characteristics are in line with that expected for application in DSSCs and are similar to several sensitizing dyes reported in the literature.Nesta tese descreve-se, inicialmente, a síntese e a caracterização fotofísica de novos corantes derivados de sulfetos, sulfóxidos e sulfonas vinílicas. Os compostos em questão foram obtidos em bons rendimentos e boa diastereosseletividade, através de reações de Horner-Wadsworth-Emmons (HWE). As propriedades fotofísicas dos corantes estudados mostraram-se bastante interessantes. Os compostos absorvem luz na região do UV/Vis, sendo que as principais transições ocorrem entre orbitais – *. Quanto a emissão, os sulfetos vinílicos PS-1 e PS-2 têm suas bandas máximas de emissão na região azul do espectro. A oxidação para seus respectivos sulfóxidos e sulfonas, e a obtenção de estrutura do tipo D– –A, faz com que a emissão sofra um deslocamento batocrômico para a região verde do espectro. Estes efeitos são mais acentuados nos derivados da trifenilamina (PSO-1 e PSO2-1) e em solvente polares (solvatocromismo positivo). Com o auxílio de cálculos DFT e TD-DFT, pode-se constatar que estes comportamentos estão relacionados à formação de estados de transferência de carga intramolecular (ICT) no estado excitado. Posteriormente, são apresentados o design, síntese e caracterização de novos sulfetos vinílicos para possível aplicação em células solares sensibilizadas (DSSCs). Os compostos foram desenhados para possuírem estrutura do D– –A, onde os sulfetos vinílicos serviriam como uma “ponte” -conjugada para os blocos doador (D) e aceptor (A). Os compostos estudados foram obtidos através da reação de HWE e condensação de Knoevenagel, em bons rendimentos e boa diastereosseletividade. Através da análise fotofísica preliminar, observou-se que os corantes possuem uma ampla faixa de absorção de luz (250– 550 nm), sobretudo os corantes derivados da malononitrila PCN-1, PCN-2 e PSCN. Além de serem bastante influenciados pela natureza do grupo aceptor de elétrons. Estas características estão de acordo com o esperado para aplicação em DSSCs e, são semelhantes a diversos corantes sensibilizadores reportados na literatura.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqporUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessSulfetos vinílicosD– -AFluorescênciaDSSCsVinyl SulphidesFluorescenceCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICANovos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicasNovel vinyl sulfides-based molecular dyes: synthesis and photophysical propertiesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisSilveira, Claudio da Cruzhttp://lattes.cnpq.br/6152568411858220Rodembusch, Fabiano Severohttp://lattes.cnpq.br/8307866489971127Mostardeiro, Marco Aureliohttp://lattes.cnpq.br/6195396264565980Rodrigues, Oscar Endrigo Dorneleshttp://lattes.cnpq.br/6536519955416085Gariani, Rogério Aparecidohttp://lattes.cnpq.br/7296497637303200http://lattes.cnpq.br/8777189789074240Araujo, Matias Monçalves1006000000006003be6a9b9-f9d9-448f-9487-6074331b34a1469e6791-270b-451c-987c-e831c7aa4f9eea55d40f-9535-4f2c-8f19-ef0d815baf7ce428c287-1542-4baf-bacc-c71aa65fc73ae7f4492f-46f8-436e-b78d-5bee588e11e448ca3883-3fe4-4e29-b2b6-6f6985248499reponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGQUIMICA_2017_ARAUJO_MATIAS.pdfTES_PPGQUIMICA_2017_ARAUJO_MATIAS.pdfTese de Doutoradoapplication/pdf8507533http://repositorio.ufsm.br/bitstream/1/12761/1/TES_PPGQUIMICA_2017_ARAUJO_MATIAS.pdf4e29d56c9e75acc1c50a632a290d03ffMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; 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dc.title.por.fl_str_mv |
Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas |
dc.title.alternative.eng.fl_str_mv |
Novel vinyl sulfides-based molecular dyes: synthesis and photophysical properties |
title |
Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas |
spellingShingle |
Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas Araujo, Matias Monçalves Sulfetos vinílicos D– -A Fluorescência DSSCs Vinyl Sulphides Fluorescence CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas |
title_full |
Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas |
title_fullStr |
Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas |
title_full_unstemmed |
Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas |
title_sort |
Novos corantes moleculares derivados de sulfetos vinílicos: síntese e propriedades fotofísicas |
author |
Araujo, Matias Monçalves |
author_facet |
Araujo, Matias Monçalves |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Silveira, Claudio da Cruz |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/6152568411858220 |
dc.contributor.referee1.fl_str_mv |
Rodembusch, Fabiano Severo |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/8307866489971127 |
dc.contributor.referee2.fl_str_mv |
Mostardeiro, Marco Aurelio |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/6195396264565980 |
dc.contributor.referee3.fl_str_mv |
Rodrigues, Oscar Endrigo Dorneles |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/6536519955416085 |
dc.contributor.referee4.fl_str_mv |
Gariani, Rogério Aparecido |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/7296497637303200 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/8777189789074240 |
dc.contributor.author.fl_str_mv |
Araujo, Matias Monçalves |
contributor_str_mv |
Silveira, Claudio da Cruz Rodembusch, Fabiano Severo Mostardeiro, Marco Aurelio Rodrigues, Oscar Endrigo Dorneles Gariani, Rogério Aparecido |
dc.subject.por.fl_str_mv |
Sulfetos vinílicos D– -A Fluorescência DSSCs |
topic |
Sulfetos vinílicos D– -A Fluorescência DSSCs Vinyl Sulphides Fluorescence CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Vinyl Sulphides Fluorescence |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This thesis describes, initially, the synthesis and photophysical characterization of new sulfides,sulphoxides and vinyl sulfones based dyes. The compounds in question were obtained in good yields and good diastereoselectivity through Horner-Wadsworth- Emmons (HWE) reactions. The compounds absorb light in the UV/Vis region, with the major transitions occurring between – * orbitals. As for the emission, the PS-1 and PS- 2 vinyl sulphides have their maximum emission bands in the blue region of the spectrum. The oxidation to their respective sulphoxides and sulfones, and the attainment of D– –A structure, causes the emission to undergo a bathochromic shift to the green region of the spectrum. These effects are most pronounced in the triphenylamine derivatives (PSO-1 and PSO2-1) and in polar solvents (positive solvatocromism). With the aid of DFT and TD-DFT calculations, it can be observed that this behaviors are related to the formation of intramolecular charge transfer states (ICT) in the excited state. Subsequently, the design, synthesis and characterization of new vinyl sulphides for possible application in dye-sensitized solar cell (DSSCs) are presented. The compounds were designed to have a D– –A structure, where the sulphides would serve as a bridge between the donor (D) and acceptor (A) blocks. The compounds studied were obtained by the HWE and Knoevenagel condensation, in good yields and good diastereoselectivity. Through preliminary photophysical analysis, it has been observed that the dyes have a wide light absorption range (250–550 nm), in particular the dyes derived from malononitrile PCN-1, PCN-2 and PSCN. In addition to being greatly influenced by the nature of the electron acceptor group. These characteristics are in line with that expected for application in DSSCs and are similar to several sensitizing dyes reported in the literature. |
publishDate |
2017 |
dc.date.issued.fl_str_mv |
2017 |
dc.date.accessioned.fl_str_mv |
2018-03-20T14:12:34Z |
dc.date.available.fl_str_mv |
2018-03-20T14:12:34Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
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doctoralThesis |
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publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/12761 |
url |
http://repositorio.ufsm.br/handle/1/12761 |
dc.language.iso.fl_str_mv |
por |
language |
por |
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100600000000 |
dc.relation.confidence.fl_str_mv |
600 |
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dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
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