p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis

Sixteen p-phenylenevinylene oligomers (OPVs) substituted with different electron-donating (ED) and electron-withdrawing (EW) groups were synthesized by the Mizoroki-Heck cross coupling reaction in moderate to good yields (40-95%), and with a totally trans-trans configuration in the vinyl bonds, whic...

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Autores:
Estrada Flórez, Sandra Elizabeth
Tipo de recurso:
Doctoral thesis
Fecha de publicación:
2017
Institución:
Universidad Nacional de Colombia
Repositorio:
Universidad Nacional de Colombia
Idioma:
spa
OAI Identifier:
oai:repositorio.unal.edu.co:unal/62838
Acceso en línea:
https://repositorio.unal.edu.co/handle/unal/62838
http://bdigital.unal.edu.co/62078/
Palabra clave:
54 Química y ciencias afines / Chemistry
62 Ingeniería y operaciones afines / Engineering
Phenylenevinylene systems
Mizoroki-Heck reaction
Optoelectronic properties
Photoredox catalysis
Dehalogenation
Hydroxylation
Aza-Henry reaction
Rights
openAccess
License
Atribución-NoComercial 4.0 Internacional
id UNACIONAL2_72c700b0919fafb56abcd50915cd4737
oai_identifier_str oai:repositorio.unal.edu.co:unal/62838
network_acronym_str UNACIONAL2
network_name_str Universidad Nacional de Colombia
repository_id_str
dc.title.spa.fl_str_mv p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis
title p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis
spellingShingle p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis
54 Química y ciencias afines / Chemistry
62 Ingeniería y operaciones afines / Engineering
Phenylenevinylene systems
Mizoroki-Heck reaction
Optoelectronic properties
Photoredox catalysis
Dehalogenation
Hydroxylation
Aza-Henry reaction
title_short p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis
title_full p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis
title_fullStr p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis
title_full_unstemmed p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis
title_sort p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis
dc.creator.fl_str_mv Estrada Flórez, Sandra Elizabeth
dc.contributor.author.spa.fl_str_mv Estrada Flórez, Sandra Elizabeth
dc.contributor.spa.fl_str_mv Sierra Ávila, Cesar Augusto
dc.subject.ddc.spa.fl_str_mv 54 Química y ciencias afines / Chemistry
62 Ingeniería y operaciones afines / Engineering
topic 54 Química y ciencias afines / Chemistry
62 Ingeniería y operaciones afines / Engineering
Phenylenevinylene systems
Mizoroki-Heck reaction
Optoelectronic properties
Photoredox catalysis
Dehalogenation
Hydroxylation
Aza-Henry reaction
dc.subject.proposal.spa.fl_str_mv Phenylenevinylene systems
Mizoroki-Heck reaction
Optoelectronic properties
Photoredox catalysis
Dehalogenation
Hydroxylation
Aza-Henry reaction
description Sixteen p-phenylenevinylene oligomers (OPVs) substituted with different electron-donating (ED) and electron-withdrawing (EW) groups were synthesized by the Mizoroki-Heck cross coupling reaction in moderate to good yields (40-95%), and with a totally trans-trans configuration in the vinyl bonds, which is difficult to obtain following common synthetic methodologies. Their structures were stablished by spectroscopic methods (FT-IR, 1H, 13C and Solid-State NMR), elemental analysis, and by mass spectrometry (MALDI-MS). The effect of the molecular structure on the optical properties was studied by UV-vis and fluorescence spectroscopies. The ED and EW groups at the ends of OPVs lead to a bathochromic shift with trends associated to the electronic nature of the substituents, effect that is intensified with the introduction of methoxy groups on the central ring. These groups also influence other properties such as the HOMO-LUMO gaps (E) and the fluorescence quantum yields (f). The most appropriate OPVs were evaluated as photoredox catalysts in synthetic reactions: a) the dehalogenation of vicinal dibromides, b) the aza-Henry reaction and, c) the hydroxylation of aryl boronic acids. Results showed that the OPVs have photoinduced electron transfer (PET) properties, being active in reduction reactions favored by ED-OPVs, and oxidation reactions favored by EW-OPVs. However, these trends could change when species such as amines and reactive oxygen species are present. This work contributes to the understanding of these important compounds and to the developing of new metal-free photoredox catalysts, providing insights about the structural features that polymeric analogs must have in order to get high efficiencies in this application.
publishDate 2017
dc.date.issued.spa.fl_str_mv 2017-05-25
dc.date.accessioned.spa.fl_str_mv 2019-07-02T21:15:18Z
dc.date.available.spa.fl_str_mv 2019-07-02T21:15:18Z
dc.type.spa.fl_str_mv Trabajo de grado - Doctorado
dc.type.driver.spa.fl_str_mv info:eu-repo/semantics/doctoralThesis
dc.type.version.spa.fl_str_mv info:eu-repo/semantics/acceptedVersion
dc.type.coar.spa.fl_str_mv http://purl.org/coar/resource_type/c_db06
dc.type.content.spa.fl_str_mv Text
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dc.identifier.uri.none.fl_str_mv https://repositorio.unal.edu.co/handle/unal/62838
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url https://repositorio.unal.edu.co/handle/unal/62838
http://bdigital.unal.edu.co/62078/
dc.language.iso.spa.fl_str_mv spa
language spa
dc.relation.ispartof.spa.fl_str_mv Universidad Nacional de Colombia Sede Bogotá Facultad de Ciencias Departamento de Química
Departamento de Química
dc.relation.references.spa.fl_str_mv Estrada Flórez, Sandra Elizabeth (2017) p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis. Doctorado thesis, Universidad Nacional de Colombia - Sede Bogotá.
dc.rights.spa.fl_str_mv Derechos reservados - Universidad Nacional de Colombia
dc.rights.coar.fl_str_mv http://purl.org/coar/access_right/c_abf2
dc.rights.license.spa.fl_str_mv Atribución-NoComercial 4.0 Internacional
dc.rights.uri.spa.fl_str_mv http://creativecommons.org/licenses/by-nc/4.0/
dc.rights.accessrights.spa.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv Atribución-NoComercial 4.0 Internacional
Derechos reservados - Universidad Nacional de Colombia
http://creativecommons.org/licenses/by-nc/4.0/
http://purl.org/coar/access_right/c_abf2
eu_rights_str_mv openAccess
dc.format.mimetype.spa.fl_str_mv application/pdf
institution Universidad Nacional de Colombia
bitstream.url.fl_str_mv https://repositorio.unal.edu.co/bitstream/unal/62838/1/SandraE.EstradaFl%c3%b3rez.2017.pdf
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repository.name.fl_str_mv Repositorio Institucional Universidad Nacional de Colombia
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spelling Atribución-NoComercial 4.0 InternacionalDerechos reservados - Universidad Nacional de Colombiahttp://creativecommons.org/licenses/by-nc/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Sierra Ávila, Cesar AugustoEstrada Flórez, Sandra Elizabeth8e7c3a52-1dc9-453d-be2e-46bac6c09d643002019-07-02T21:15:18Z2019-07-02T21:15:18Z2017-05-25https://repositorio.unal.edu.co/handle/unal/62838http://bdigital.unal.edu.co/62078/Sixteen p-phenylenevinylene oligomers (OPVs) substituted with different electron-donating (ED) and electron-withdrawing (EW) groups were synthesized by the Mizoroki-Heck cross coupling reaction in moderate to good yields (40-95%), and with a totally trans-trans configuration in the vinyl bonds, which is difficult to obtain following common synthetic methodologies. Their structures were stablished by spectroscopic methods (FT-IR, 1H, 13C and Solid-State NMR), elemental analysis, and by mass spectrometry (MALDI-MS). The effect of the molecular structure on the optical properties was studied by UV-vis and fluorescence spectroscopies. The ED and EW groups at the ends of OPVs lead to a bathochromic shift with trends associated to the electronic nature of the substituents, effect that is intensified with the introduction of methoxy groups on the central ring. These groups also influence other properties such as the HOMO-LUMO gaps (E) and the fluorescence quantum yields (f). The most appropriate OPVs were evaluated as photoredox catalysts in synthetic reactions: a) the dehalogenation of vicinal dibromides, b) the aza-Henry reaction and, c) the hydroxylation of aryl boronic acids. Results showed that the OPVs have photoinduced electron transfer (PET) properties, being active in reduction reactions favored by ED-OPVs, and oxidation reactions favored by EW-OPVs. However, these trends could change when species such as amines and reactive oxygen species are present. This work contributes to the understanding of these important compounds and to the developing of new metal-free photoredox catalysts, providing insights about the structural features that polymeric analogs must have in order to get high efficiencies in this application.Abstract. Dieciséis oligo(p-fenilenvinileno)s (OFVs), sustituidos con diferentes grupos electrodonores y electroaceptores fueron sintetizados por reacción de acoplamiento cruzado de Mizoroki-Heck con rendimientos de moderados a buenos (40-95%), con una configuración de los enlaces vinílicos totalmente trans-trans, la cual es difícil de obtener siguiendo metodologías comunes. Sus estructuras fueron establecidas por métodos espectroscópicos (FT-IR y RMN 1H, 13C y en estado sólido), análisis elemental y espectrometría de masas (MALDI-MS). El efecto de la estructura en las propiedades ópticas fue estudiado por UV-vis y espectroscopia de fluorescencia. Los grupos en los anillos terminales de los OFVs, conllevaron a corrimientos batocrómicos con tendencias asociadas a la naturaleza electrónica de los sustituyentes, efecto que fue intensificado con la introducción de grupos metoxilo en el anillo central. Estos grupos también tienen influencia en propiedades como la diferencia de energía HOMO-LUMO (E) y los rendimientos cuánticos de fluorescencia (f). Los OFVs más apropiados fueron evaluados como catalizadores fotoredox en reacciones de síntesis: a) la deshalogenación de dibromuros vecinales, b) la reacción aza-Henry, c) la hidroxilación de ácidos arilborónicos. Los resultados mostraron que los OFVs tienen propiedades de transferencia de carga fotoinducida, siendo activos en reacciones de reducción favorecidas por ED-OFVs y de oxidación favorecidas por EW-OFVs. Tendencia que puede cambiar con la presencia de aminas y especies reactivas de oxígeno. Este trabajo contribuye al entendimiento de estos importantes materiales y al desarrollo de catalizadores fotoredox libres de metales, proporcionando ideas sobre las características estructurales que los análogos poliméricos deben tener para tener altas eficiencias en esta aplicación.Doctoradoapplication/pdfspaUniversidad Nacional de Colombia Sede Bogotá Facultad de Ciencias Departamento de QuímicaDepartamento de QuímicaEstrada Flórez, Sandra Elizabeth (2017) p-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesis. Doctorado thesis, Universidad Nacional de Colombia - Sede Bogotá.54 Química y ciencias afines / Chemistry62 Ingeniería y operaciones afines / EngineeringPhenylenevinylene systemsMizoroki-Heck reactionOptoelectronic propertiesPhotoredox catalysisDehalogenationHydroxylationAza-Henry reactionp-Phenylenevinylene oligomers with application as photoredox catalysts in organic synthesisTrabajo de grado - Doctoradoinfo:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/acceptedVersionhttp://purl.org/coar/resource_type/c_db06Texthttp://purl.org/redcol/resource_type/TDORIGINALSandraE.EstradaFlórez.2017.pdfapplication/pdf15205279https://repositorio.unal.edu.co/bitstream/unal/62838/1/SandraE.EstradaFl%c3%b3rez.2017.pdfa2b1ba02e4dec6931bfbfaf5d81f81a2MD51THUMBNAILSandraE.EstradaFlórez.2017.pdf.jpgSandraE.EstradaFlórez.2017.pdf.jpgGenerated Thumbnailimage/jpeg4702https://repositorio.unal.edu.co/bitstream/unal/62838/2/SandraE.EstradaFl%c3%b3rez.2017.pdf.jpg49c39e12c8654be29d6e0a67004a019aMD52unal/62838oai:repositorio.unal.edu.co:unal/628382024-04-25 23:14:09.747Repositorio Institucional Universidad Nacional de Colombiarepositorio_nal@unal.edu.co