Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida

Detalhes bibliográficos
Autor(a) principal: Queiroga, Anna Paula Rocha de
Data de Publicação: 2021
Tipo de documento: Dissertação
Idioma: por
Título da fonte: Biblioteca Digital de Teses e Dissertações da UFPB
Texto Completo: https://repositorio.ufpb.br/jspui/handle/123456789/20247
Resumo: The coordination compounds of trivalent lanthanide ions are widely studied due to their peculiar photophysical properties that allow their use in several applications. To this end, it is of utmost importance to study and determine ligand that are efficient for the luminescence sensitization process of these ions. With this in mind, this study reports the synthesis of a new class of complex tris β-diketonates of the Eu3+ ion and its Gd3+ analogues with the compound 2-(1,3-dioxoisoindoline-2-yl)-N-(pyridin-2-yl)acetamide (fg2ap) as an auxiliary binder, aiming to investigate its photoluminescent properties. The auxiliary ligand amide was initiated from the reaction between 2-aminopyridine and N-phthaloylglycine chloride in a yield of 56,18%. The determination of ligand synthesis was made by melting point data, absorption spectroscopy in the infrared region and 1H and 13C nuclear magnetic resonance. The complexes, on the other hand, were synthesized by replacing the water molecules of the hydrated tris β-diketonate complexes with the amide ligand fg2ap, presenting yields of 26 to 83%. These were characterized by complexometric titration, spectroscopy in the infrared region, thermogravimetric analysis and had their spectroscopic properties were analyzed experimentally, as well as geometries and absorption spectra investigated from computational modeling. The data captured by complexometric titration and thermogravimetric analysis suggest that the complexes have a general formula [Ln(β-dic)3(fg2ap)], and the coordination of the β-dicetonate ligands occurs through the oxygen atoms of the carbonyl groups and the auxiliary ligand amide by means of one of the carbonyls and heterocyclic nitrogen, according to the absorption spectra in the infrared region. The replacement of water molecules by this amide in the Eu3+ ion complexes increases the intrinsic quantum yields of luminescence and the triplet states determined experimentally through the emission spectra of the Gd3+ complexes, as well as, according to the TDDFT calculations of excited states, indicate favorable resonance conditions between the lowest energy triplet states of the ligands with the 5D0 emitter level of the Eu3+ ion.
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spelling Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamidaLuminescênciaβ-dicetonasAmidas como ligantesTransferência de energia.Luminescenceβ-diketonesAmides as ligandsEnergy transferCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAThe coordination compounds of trivalent lanthanide ions are widely studied due to their peculiar photophysical properties that allow their use in several applications. To this end, it is of utmost importance to study and determine ligand that are efficient for the luminescence sensitization process of these ions. With this in mind, this study reports the synthesis of a new class of complex tris β-diketonates of the Eu3+ ion and its Gd3+ analogues with the compound 2-(1,3-dioxoisoindoline-2-yl)-N-(pyridin-2-yl)acetamide (fg2ap) as an auxiliary binder, aiming to investigate its photoluminescent properties. The auxiliary ligand amide was initiated from the reaction between 2-aminopyridine and N-phthaloylglycine chloride in a yield of 56,18%. The determination of ligand synthesis was made by melting point data, absorption spectroscopy in the infrared region and 1H and 13C nuclear magnetic resonance. The complexes, on the other hand, were synthesized by replacing the water molecules of the hydrated tris β-diketonate complexes with the amide ligand fg2ap, presenting yields of 26 to 83%. These were characterized by complexometric titration, spectroscopy in the infrared region, thermogravimetric analysis and had their spectroscopic properties were analyzed experimentally, as well as geometries and absorption spectra investigated from computational modeling. The data captured by complexometric titration and thermogravimetric analysis suggest that the complexes have a general formula [Ln(β-dic)3(fg2ap)], and the coordination of the β-dicetonate ligands occurs through the oxygen atoms of the carbonyl groups and the auxiliary ligand amide by means of one of the carbonyls and heterocyclic nitrogen, according to the absorption spectra in the infrared region. The replacement of water molecules by this amide in the Eu3+ ion complexes increases the intrinsic quantum yields of luminescence and the triplet states determined experimentally through the emission spectra of the Gd3+ complexes, as well as, according to the TDDFT calculations of excited states, indicate favorable resonance conditions between the lowest energy triplet states of the ligands with the 5D0 emitter level of the Eu3+ ion.Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqOs compostos de coordenação de íons lantanídeos trivalentes são amplamente estudados devidos as suas peculiares propriedades fotofísicas que permitem seu uso em diversas aplicações. Para tal, é de suma importância o estudo e determinação de ligantes orgânicos que sejam eficientes para o processo de sensibilização de luminescência destes íons. Tendo isto em vista, reporta-se neste estudo a síntese de uma nova classe de complexos tris β-dicetonatos do íon Eu3+ e seus análogos de Gd3+ com o composto 2-(1,3-dioxoisoindolin-2-il)-N-(piridin-2-il)acetamida (fg2ap) como ligante auxiliar, objetivando investigar suas propriedades fotoluminescentes. O ligante auxiliar amida foi obtido a partir da reação entre a 2-aminopiridina com o cloreto de N-ftaloilglicina com um rendimento de 56,18%. A confirmação de síntese do ligante se deu por dados de ponto de fusão, espectroscopia de absorção na região do infravermelho e ressonância magnética nuclear de 1H e 13C. Já os complexos, foram sintetizados a partir da substituição das moléculas de água dos complexos tris β-dicetonatos hidratados pelo ligante amida fg2ap, apresentando rendimentos de 26 a 83%. Estes foram caracterizados por titulação complexométrica, espectroscopia na região do infravermelho, análise termogravimétrica e tiveram suas propriedades espectroscópicas analisadas experimentalmente, como também, geometrias e espectros de absorção investigados a partir de modelagem computacional. Os dados obtidos por titulação complexométrica e análise termogravimétrica sugerem que os complexos apresentam fórmula geral [Ln(β-dic)3(fg2ap)], sendo que a coordenação dos ligantes β-dicetonatos ocorre por meio dos átomos de oxigênio dos grupos carbonilas e do ligante auxiliar fg2ap por meio de uma das carbonilas e do nitrogênio heterocíclico, de acordo com os espectros de absorção na região do infravermelho. A substituição de moléculas de água por essa amida nos complexos do íon Eu3+ aumenta os rendimentos quânticos intrínsecos da luminescência. Os estados tripletos determinados experimentalmente através dos espectros de emissão dos complexos de Gd3+, como também, segundo os cálculos TDDFT de estados excitados, indicam condições de ressonância favoráveis entre os estados tripletos de mais baixa energia dos ligantes com o nível emissor 5D0 do íon Eu3+.Universidade Federal da ParaíbaBrasilQuímicaPrograma de Pós-Graduação em QuímicaUFPBFaustino, Wagner de Mendonçahttp://lattes.cnpq.br/4969484654273225Lira, Bruno Freitashttp://lattes.cnpq.br/3555982568650926Queiroga, Anna Paula Rocha de2021-06-29T14:34:55Z2021-02-022021-06-29T14:34:55Z2021-01-25info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesishttps://repositorio.ufpb.br/jspui/handle/123456789/20247porhttp://creativecommons.org/licenses/by-nd/3.0/br/info:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações da UFPBinstname:Universidade Federal da Paraíba (UFPB)instacron:UFPB2022-08-10T11:50:35Zoai:repositorio.ufpb.br:123456789/20247Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufpb.br/PUBhttp://tede.biblioteca.ufpb.br:8080/oai/requestdiretoria@ufpb.br|| diretoria@ufpb.bropendoar:2022-08-10T11:50:35Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB)false
dc.title.none.fl_str_mv Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida
title Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida
spellingShingle Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida
Queiroga, Anna Paula Rocha de
Luminescência
β-dicetonas
Amidas como ligantes
Transferência de energia.
Luminescence
β-diketones
Amides as ligands
Energy transfer
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
title_short Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida
title_full Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida
title_fullStr Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida
title_full_unstemmed Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida
title_sort Síntese e estudo das propriedades fotoluminescentes de novos complexos β-dicetonatos do íon Eu3+ com o ligante 2-(1,3-dioxoisoindolin-2-il)-n-(piridin-2-il) acetamida
author Queiroga, Anna Paula Rocha de
author_facet Queiroga, Anna Paula Rocha de
author_role author
dc.contributor.none.fl_str_mv Faustino, Wagner de Mendonça
http://lattes.cnpq.br/4969484654273225
Lira, Bruno Freitas
http://lattes.cnpq.br/3555982568650926
dc.contributor.author.fl_str_mv Queiroga, Anna Paula Rocha de
dc.subject.por.fl_str_mv Luminescência
β-dicetonas
Amidas como ligantes
Transferência de energia.
Luminescence
β-diketones
Amides as ligands
Energy transfer
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
topic Luminescência
β-dicetonas
Amidas como ligantes
Transferência de energia.
Luminescence
β-diketones
Amides as ligands
Energy transfer
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA
description The coordination compounds of trivalent lanthanide ions are widely studied due to their peculiar photophysical properties that allow their use in several applications. To this end, it is of utmost importance to study and determine ligand that are efficient for the luminescence sensitization process of these ions. With this in mind, this study reports the synthesis of a new class of complex tris β-diketonates of the Eu3+ ion and its Gd3+ analogues with the compound 2-(1,3-dioxoisoindoline-2-yl)-N-(pyridin-2-yl)acetamide (fg2ap) as an auxiliary binder, aiming to investigate its photoluminescent properties. The auxiliary ligand amide was initiated from the reaction between 2-aminopyridine and N-phthaloylglycine chloride in a yield of 56,18%. The determination of ligand synthesis was made by melting point data, absorption spectroscopy in the infrared region and 1H and 13C nuclear magnetic resonance. The complexes, on the other hand, were synthesized by replacing the water molecules of the hydrated tris β-diketonate complexes with the amide ligand fg2ap, presenting yields of 26 to 83%. These were characterized by complexometric titration, spectroscopy in the infrared region, thermogravimetric analysis and had their spectroscopic properties were analyzed experimentally, as well as geometries and absorption spectra investigated from computational modeling. The data captured by complexometric titration and thermogravimetric analysis suggest that the complexes have a general formula [Ln(β-dic)3(fg2ap)], and the coordination of the β-dicetonate ligands occurs through the oxygen atoms of the carbonyl groups and the auxiliary ligand amide by means of one of the carbonyls and heterocyclic nitrogen, according to the absorption spectra in the infrared region. The replacement of water molecules by this amide in the Eu3+ ion complexes increases the intrinsic quantum yields of luminescence and the triplet states determined experimentally through the emission spectra of the Gd3+ complexes, as well as, according to the TDDFT calculations of excited states, indicate favorable resonance conditions between the lowest energy triplet states of the ligands with the 5D0 emitter level of the Eu3+ ion.
publishDate 2021
dc.date.none.fl_str_mv 2021-06-29T14:34:55Z
2021-02-02
2021-06-29T14:34:55Z
2021-01-25
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/masterThesis
format masterThesis
status_str publishedVersion
dc.identifier.uri.fl_str_mv https://repositorio.ufpb.br/jspui/handle/123456789/20247
url https://repositorio.ufpb.br/jspui/handle/123456789/20247
dc.language.iso.fl_str_mv por
language por
dc.rights.driver.fl_str_mv http://creativecommons.org/licenses/by-nd/3.0/br/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nd/3.0/br/
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Universidade Federal da Paraíba
Brasil
Química
Programa de Pós-Graduação em Química
UFPB
publisher.none.fl_str_mv Universidade Federal da Paraíba
Brasil
Química
Programa de Pós-Graduação em Química
UFPB
dc.source.none.fl_str_mv reponame:Biblioteca Digital de Teses e Dissertações da UFPB
instname:Universidade Federal da Paraíba (UFPB)
instacron:UFPB
instname_str Universidade Federal da Paraíba (UFPB)
instacron_str UFPB
institution UFPB
reponame_str Biblioteca Digital de Teses e Dissertações da UFPB
collection Biblioteca Digital de Teses e Dissertações da UFPB
repository.name.fl_str_mv Biblioteca Digital de Teses e Dissertações da UFPB - Universidade Federal da Paraíba (UFPB)
repository.mail.fl_str_mv diretoria@ufpb.br|| diretoria@ufpb.br
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