Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas
Autor(a) principal: | |
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Data de Publicação: | 2022 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Manancial - Repositório Digital da UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/26730 |
Resumo: | This work presents the synthesis and studies of photophysical and electrochemical behaviour of new phenothiazines derivatives containing the vinyl-chalcogenyl group in different positions of the heterocyclic. This research starts from the assumption that the sulphur atom behaves as a bridge between conjugated structures and can be used on the synthesis of highly conjugated dyes. Its oxidation can lead to compounds with more interesting properties due to the insertion of strong electron-withdrawing groups. Phenothiazine is also an important core on material chemistry because it presents interesting photophysical and optical properties, which can be tuned by modification in its structure. Therefore, the objective of this work was to analyse the effect of the structure modification on the photophysical and electrochemical properties by adding the groups vinyl-chalcogenyl in different positions of phenothiazine. The compounds studied in this work were synthesized via Wittig-Horner reaction and were obtained with high yields (67 to 94%), short reaction times, maximum of 3.5 h, and with good stereoselectivity for the non-oxidate compounds. The sulfoxide was obtained in a mixture of E:Z of 17:1 and just isomer E was obtained on the synthesis of sulfones. Through this studies, it was found that the resonance effects at position 10 of phenothiazine are impaired due to the intra conformation that the structure acquires, resulting from the steric hindrance effect between the tricyclic ring and the ring at position 10. Thus, these derivatives have quantum yields of fluorescence relatively lower (from 0.03 to 0.12) compared to 3-substituted phenothiazines (from 0.13 to 0.90), despite having higher Stokes Shift. The change in the size of the alkyl chain at position 10 did not result in significantly differences in the properties of the compounds. However, the exchange of sulphur atom for selenium resulted in a decrease in fluorescence, a fact caused by the effect of the heavy atom. Advancing with the studies, the increase in the conjugated system when adding two phenothiazines or two vinylic moieties caused a bathochromic effect on the absorption of the compounds, of around 20 nm, but did not increase the fluorescence quantum yield. The oxidation of sulphur to sulfoxide and sulfone resulted in red shifted emission spectra due to the more pronounced electron-withdrawing effect of these groups. On the other hand, the quantum yield and the Stokes shift were similar between the compounds, indicating that simple structures also have interesting properties. Electrochemical studies have shown that the compounds have relatively low oxidation and reduction potentials, which are dependent on the electron-withdrawing fraction. In this way, they present an amphoteric character, important for later application of these compounds in LEDs, organic photovoltaics and in catalysis. |
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Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicasNew dyes derived from vinyl-chalcogenyl phenothiazines: synthesis and studies of the photophysical and electrochemical propertiesFenotiazinaCalcogenetos vinílicosFotofísicaFluorescênciaEletroquímicaPhenothiazineVinyl chalcogenidesPhotophysicsFluorescenceElectrochemistryCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThis work presents the synthesis and studies of photophysical and electrochemical behaviour of new phenothiazines derivatives containing the vinyl-chalcogenyl group in different positions of the heterocyclic. This research starts from the assumption that the sulphur atom behaves as a bridge between conjugated structures and can be used on the synthesis of highly conjugated dyes. Its oxidation can lead to compounds with more interesting properties due to the insertion of strong electron-withdrawing groups. Phenothiazine is also an important core on material chemistry because it presents interesting photophysical and optical properties, which can be tuned by modification in its structure. Therefore, the objective of this work was to analyse the effect of the structure modification on the photophysical and electrochemical properties by adding the groups vinyl-chalcogenyl in different positions of phenothiazine. The compounds studied in this work were synthesized via Wittig-Horner reaction and were obtained with high yields (67 to 94%), short reaction times, maximum of 3.5 h, and with good stereoselectivity for the non-oxidate compounds. The sulfoxide was obtained in a mixture of E:Z of 17:1 and just isomer E was obtained on the synthesis of sulfones. Through this studies, it was found that the resonance effects at position 10 of phenothiazine are impaired due to the intra conformation that the structure acquires, resulting from the steric hindrance effect between the tricyclic ring and the ring at position 10. Thus, these derivatives have quantum yields of fluorescence relatively lower (from 0.03 to 0.12) compared to 3-substituted phenothiazines (from 0.13 to 0.90), despite having higher Stokes Shift. The change in the size of the alkyl chain at position 10 did not result in significantly differences in the properties of the compounds. However, the exchange of sulphur atom for selenium resulted in a decrease in fluorescence, a fact caused by the effect of the heavy atom. Advancing with the studies, the increase in the conjugated system when adding two phenothiazines or two vinylic moieties caused a bathochromic effect on the absorption of the compounds, of around 20 nm, but did not increase the fluorescence quantum yield. The oxidation of sulphur to sulfoxide and sulfone resulted in red shifted emission spectra due to the more pronounced electron-withdrawing effect of these groups. On the other hand, the quantum yield and the Stokes shift were similar between the compounds, indicating that simple structures also have interesting properties. Electrochemical studies have shown that the compounds have relatively low oxidation and reduction potentials, which are dependent on the electron-withdrawing fraction. In this way, they present an amphoteric character, important for later application of these compounds in LEDs, organic photovoltaics and in catalysis.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqEste trabalho apresenta a síntese e o estudo do comportamento fotofísico e eletroquímico de novos derivados de fenotiazinas contendo o grupo vinil-calcogenil em diferentes posições do heterociclo. A pesquisa parte do pressuposto de que o átomo de enxofre se comporta como uma ponte entre estruturas conjugadas e pode ser utilizado na síntese de corantes altamente conjugados. A sua oxidação levaria a compostos com propriedades mais interessantes devido à inserção de grupos fortemente retiradores de elétrons. A fenotiazina é, também, um importante núcleo na química de materiais pois apresenta interessantes propriedades fotofísicas e ópticas que podem ser ajustadas através de modificações na sua estrutura. Desta forma, o objetivo deste trabalho foi verificar o efeito da modificação estrutural nas propriedades fotofísicas e eletroquímicas ao adicionar grupos vinil-calcogenil em diferentes posições da fenotiazina. Os compostos estudados neste trabalho foram sintetizados através de reação de Wittig-Horner e foram obtidos com rendimentos de 67% a 94%, em curto período de tempo, de no máximo 3,5 h, e com boa estereosseletividade para os compostos não oxidados. O sulfóxido foi obtido em uma mistura E:Z de 17:1 e apenas o isômero E foi obtido na síntese das sulfonas. Por meio deste estudo, foi verificado que os efeitos de ressonância na posição 10 da fenotiazina são prejudicados devido à conformação intra que a estrutura adquire, resultante do efeito de impedimento estérico entre o anel do triciclo e o anel na posição 10. Desta forma, estes derivados possuem rendimentos quânticos de fluorescência relativamente mais baixos (de 0,03 a 0,12) em comparação às fenotiazinas 3-substituídas (de 0,13 a 0,90), apesar de possuírem Deslocamento de Stokes superiores. A mudança no tamanho da cadeia alquílica na posição 10 não trouxe diferenças significantes nas propriedades dos compostos. Porém, a troca do átomo de enxofre pelo selênio resultou em uma diminuição da fluorescência, fato causado pelo efeito do átomo pesado. Em continuidade aos estudos, o aumento do sistema conjugado ao se adicionar duas porções fenotiazinas ou duas porções vinílicas, ocasionou um efeito batocrômico na absorção dos compostos em torno de 20 nm, mas não aumentou o rendimento quântico de fluorescência. A oxidação do enxofre para sulfóxido e sulfona resultou em espectros de emissão deslocados para o vermelho devido ao efeito retirador de elétrons mais pronunciado destes grupos. Entretanto, o rendimento quântico e o Deslocamento de Stokes foram similares entre os compostos, indicando que estruturas simples também apresentam propriedades interessantes. Os estudos eletroquímicos demonstraram que os compostos apresentam potenciais de oxidação e redução relativamente baixos e dependentes da fração retiradora de elétrons. Desta forma, apresentam um caráter anfotérico, importante para posterior aplicação destes compostos em LEDs, fotovoltaicos orgânicos e em catálise.Universidade Federal de Santa MariaBrasilQuímicaUFSMPrograma de Pós-Graduação em QuímicaCentro de Ciências Naturais e ExatasSilveira, Claudio da Cruzhttp://lattes.cnpq.br/6152568411858220Schumacher, Ricardo FredericoIglesias, Bernardo AlmeidaLenardão, Eder JoãoScaranaro, Filipe Vinicius PenteadoPerin, GelsonDilelio, Marina Cardoso2022-11-01T15:18:28Z2022-11-01T15:18:28Z2022-10-21info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisapplication/pdfhttp://repositorio.ufsm.br/handle/1/26730porAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessreponame:Manancial - Repositório Digital da UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSM2022-11-01T15:18:28Zoai:repositorio.ufsm.br:1/26730Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2024-07-29T10:42:56.153846Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.none.fl_str_mv |
Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas New dyes derived from vinyl-chalcogenyl phenothiazines: synthesis and studies of the photophysical and electrochemical properties |
title |
Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas |
spellingShingle |
Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas Dilelio, Marina Cardoso Fenotiazina Calcogenetos vinílicos Fotofísica Fluorescência Eletroquímica Phenothiazine Vinyl chalcogenides Photophysics Fluorescence Electrochemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas |
title_full |
Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas |
title_fullStr |
Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas |
title_full_unstemmed |
Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas |
title_sort |
Novos corantes derivados de vinil-calcogenil fenotiazinas: síntese e estudo das propriedades fotofísicas e eletroquímicas |
author |
Dilelio, Marina Cardoso |
author_facet |
Dilelio, Marina Cardoso |
author_role |
author |
dc.contributor.none.fl_str_mv |
Silveira, Claudio da Cruz http://lattes.cnpq.br/6152568411858220 Schumacher, Ricardo Frederico Iglesias, Bernardo Almeida Lenardão, Eder João Scaranaro, Filipe Vinicius Penteado Perin, Gelson |
dc.contributor.author.fl_str_mv |
Dilelio, Marina Cardoso |
dc.subject.por.fl_str_mv |
Fenotiazina Calcogenetos vinílicos Fotofísica Fluorescência Eletroquímica Phenothiazine Vinyl chalcogenides Photophysics Fluorescence Electrochemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
topic |
Fenotiazina Calcogenetos vinílicos Fotofísica Fluorescência Eletroquímica Phenothiazine Vinyl chalcogenides Photophysics Fluorescence Electrochemistry CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work presents the synthesis and studies of photophysical and electrochemical behaviour of new phenothiazines derivatives containing the vinyl-chalcogenyl group in different positions of the heterocyclic. This research starts from the assumption that the sulphur atom behaves as a bridge between conjugated structures and can be used on the synthesis of highly conjugated dyes. Its oxidation can lead to compounds with more interesting properties due to the insertion of strong electron-withdrawing groups. Phenothiazine is also an important core on material chemistry because it presents interesting photophysical and optical properties, which can be tuned by modification in its structure. Therefore, the objective of this work was to analyse the effect of the structure modification on the photophysical and electrochemical properties by adding the groups vinyl-chalcogenyl in different positions of phenothiazine. The compounds studied in this work were synthesized via Wittig-Horner reaction and were obtained with high yields (67 to 94%), short reaction times, maximum of 3.5 h, and with good stereoselectivity for the non-oxidate compounds. The sulfoxide was obtained in a mixture of E:Z of 17:1 and just isomer E was obtained on the synthesis of sulfones. Through this studies, it was found that the resonance effects at position 10 of phenothiazine are impaired due to the intra conformation that the structure acquires, resulting from the steric hindrance effect between the tricyclic ring and the ring at position 10. Thus, these derivatives have quantum yields of fluorescence relatively lower (from 0.03 to 0.12) compared to 3-substituted phenothiazines (from 0.13 to 0.90), despite having higher Stokes Shift. The change in the size of the alkyl chain at position 10 did not result in significantly differences in the properties of the compounds. However, the exchange of sulphur atom for selenium resulted in a decrease in fluorescence, a fact caused by the effect of the heavy atom. Advancing with the studies, the increase in the conjugated system when adding two phenothiazines or two vinylic moieties caused a bathochromic effect on the absorption of the compounds, of around 20 nm, but did not increase the fluorescence quantum yield. The oxidation of sulphur to sulfoxide and sulfone resulted in red shifted emission spectra due to the more pronounced electron-withdrawing effect of these groups. On the other hand, the quantum yield and the Stokes shift were similar between the compounds, indicating that simple structures also have interesting properties. Electrochemical studies have shown that the compounds have relatively low oxidation and reduction potentials, which are dependent on the electron-withdrawing fraction. In this way, they present an amphoteric character, important for later application of these compounds in LEDs, organic photovoltaics and in catalysis. |
publishDate |
2022 |
dc.date.none.fl_str_mv |
2022-11-01T15:18:28Z 2022-11-01T15:18:28Z 2022-10-21 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/doctoralThesis |
format |
doctoralThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/26730 |
url |
http://repositorio.ufsm.br/handle/1/26730 |
dc.language.iso.fl_str_mv |
por |
language |
por |
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.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Brasil Química UFSM Programa de Pós-Graduação em Química Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Manancial - Repositório Digital da UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Manancial - Repositório Digital da UFSM |
collection |
Manancial - Repositório Digital da UFSM |
repository.name.fl_str_mv |
Manancial - Repositório Digital da UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
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1814349332947664896 |