Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas
Autor(a) principal: | |
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Data de Publicação: | 2012 |
Tipo de documento: | Tese |
Idioma: | por |
Título da fonte: | Repositório Institucional da UFSCAR |
Texto Completo: | https://repositorio.ufscar.br/handle/ufscar/6239 |
Resumo: | This thesis involves the syntheses and characterization of four heterotriads formed by metallotetraphenylporphyrins (CoTPP and NiTPP) and metallophthalocyanines (CoPc and NiPc) using pyrazine (pz) and trans-1,2-bis(4-pyridyl)ethylene (bpe) as spacer ligands. The following sequences: NiPc(pz)CoTPP(pz)NiPc, NiTPP(pz)CoPc(pz)NiTPP, NiTPP(bpe)CoPc(bpe)NiTPP and CoTPP(bpe)CoPc(bpe)CoTPP were investigated. All triads were analyzed by infrared and ultraviolet-visible spectroscopy and some of them were characterized by elemental analysis, termogravimetry and differential thermal analysis. The infrared and electronic spectra of the triads showed characteristic absorption bands of the two macrocycles. The elemental data are in a good agreement with the proposed stoichiometry of these arrays. The triad NiTPP(pz)CoPc(pz)NiTPP had its stoichiometry confirmed via thermogravimetry and elemental analysis. Besides these results, this thesis also reports the crystal structure of a new pseudopolymorph of cobalt tetraphenylporphyrin (CoTPP) obtained by single-crystal X-ray diffraction. This non-stoichiometric solvate crystallized in the space group Pī with unit cell parameters distinct from the non-solvated CoTPP, which in general, like others metallotetraphenylporphyrins, tends to crystallize in the tetragonal space group I42d. The triclinic and tetragonal forms differ with respect to the conformation adopted by the macrocycle and also in the phenyl orientation. Crystal packing analysis of this pseudopolymorph revealed the presence of infinite channels along the a axis that are filled by dichloromethane solvent molecules, which represents therefore the first clathrate of CoTPP reported in the literature. |
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Melo, Cristiane Cabral deMoreira, Wania da Conceiçãohttp://genos.cnpq.br:12010/dwlattes/owa/prc_imp_cv_int?f_cod=K4786312J8http://lattes.cnpq.br/870204534566026457ae67ce-c899-4ff1-a529-2c98670463392016-06-02T20:34:37Z2012-10-172016-06-02T20:34:37Z2012-06-29MELO, Cristiane Cabral de. Syntheses and structural investigations of supramolecular arrays formed by metalloporphyrins and metallophthalocyanines.. 2012. 113 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2012.https://repositorio.ufscar.br/handle/ufscar/6239This thesis involves the syntheses and characterization of four heterotriads formed by metallotetraphenylporphyrins (CoTPP and NiTPP) and metallophthalocyanines (CoPc and NiPc) using pyrazine (pz) and trans-1,2-bis(4-pyridyl)ethylene (bpe) as spacer ligands. The following sequences: NiPc(pz)CoTPP(pz)NiPc, NiTPP(pz)CoPc(pz)NiTPP, NiTPP(bpe)CoPc(bpe)NiTPP and CoTPP(bpe)CoPc(bpe)CoTPP were investigated. All triads were analyzed by infrared and ultraviolet-visible spectroscopy and some of them were characterized by elemental analysis, termogravimetry and differential thermal analysis. The infrared and electronic spectra of the triads showed characteristic absorption bands of the two macrocycles. The elemental data are in a good agreement with the proposed stoichiometry of these arrays. The triad NiTPP(pz)CoPc(pz)NiTPP had its stoichiometry confirmed via thermogravimetry and elemental analysis. Besides these results, this thesis also reports the crystal structure of a new pseudopolymorph of cobalt tetraphenylporphyrin (CoTPP) obtained by single-crystal X-ray diffraction. This non-stoichiometric solvate crystallized in the space group Pī with unit cell parameters distinct from the non-solvated CoTPP, which in general, like others metallotetraphenylporphyrins, tends to crystallize in the tetragonal space group I42d. The triclinic and tetragonal forms differ with respect to the conformation adopted by the macrocycle and also in the phenyl orientation. Crystal packing analysis of this pseudopolymorph revealed the presence of infinite channels along the a axis that are filled by dichloromethane solvent molecules, which represents therefore the first clathrate of CoTPP reported in the literature.Essa tese envolve a síntese e a caracterização de quatro heterotríades constituídas por metalotetrafenilporfirinas (CoTPP e NiTPP) e metaloftalocianinas (CoPc e NiPc) usando pirazina (pz) e trans-1,2-bis(4-piridil)etileno (bpe) como ligantes espaçadores. As seguintes sequências foram investigadas: NiPc(pz)CoTPP(pz)NiPc, NiTPP(pz)CoPc(pz)NiTPP, NiTPP(bpe)CoPc(bpe)NiTPP e CoTPP(bpe)CoPc(bpe)CoTPP. Todas as tríades foram caracterizadas por espectroscopia no infravermelho e no ultravioleta-visível. Algumas delas foram analisadas por termogravimetria, análise térmica diferencial e análise elementar. Os espectros no ultravioleta-visível e no infravermelho das tríades mostraram bandas de absorção características dos dois macrociclos. Os dados da análise elementar exibiram uma boa correlação com a estequiometria proposta para esses arranjos. A tríade NiTPP(pz)CoPc(pz)NiTPP teve a sua estequiometria confirmada por análise elementar e termogravimétrica. Além desses resultados, essa tese também reporta a estrutura cristalográfica de um novo pseudopolimorfo da cobaltotetrafenilporfirina (CoTPP) obtido por difração de raios X por monocristal. Esse solvato não estequiométrico cristalizou no grupo espacial Pī com parâmetros de cela distintos da forma não solvatada da CoTPP, a qual em geral, assim como outras metalotetrafenilporfirinas, tendem a cristalizar no grupo espacial tetragonal I42d. Além das diferenças conformacionais adotadas pelo macrociclo, as formas triclínica e tetragonal da CoTPP também diferem em relação a orientação das fenilas. A análise do empacotamento cristalino desse pseudopolimorfo revelou a formação de infinitos canais paralelos ao eixo a, preenchidos por moléculas do solvente diclorometano, constituindo o primeiro clatrato de CoTPP reportado na literatura.Universidade Federal de Minas Geraisapplication/pdfporUniversidade Federal de São CarlosPrograma de Pós-Graduação em Química - PPGQUFSCarBRQuímica inorgânicaSínteseArranjos supramoleculares mistosMetaloporfirinasMetaloftalocianinaClatratoMetallotetraphenylporphyrinsMetallophthalocyaninesMixed tetrapirrolic arraysClathrateCIENCIAS EXATAS E DA TERRA::QUIMICASíntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinasSyntheses and structural investigations of supramolecular arrays formed by metalloporphyrins and metallophthalocyanines.info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesis-1-189942258-47c3-45f6-8ba5-2f6976d8a328info:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFSCARinstname:Universidade Federal de São Carlos (UFSCAR)instacron:UFSCARORIGINAL4600.pdfapplication/pdf3262099https://repositorio.ufscar.br/bitstream/ufscar/6239/1/4600.pdf1b7e10bcd82d9c791f13376725a1f80fMD51TEXT4600.pdf.txt4600.pdf.txtExtracted texttext/plain0https://repositorio.ufscar.br/bitstream/ufscar/6239/4/4600.pdf.txtd41d8cd98f00b204e9800998ecf8427eMD54THUMBNAIL4600.pdf.jpg4600.pdf.jpgIM Thumbnailimage/jpeg9448https://repositorio.ufscar.br/bitstream/ufscar/6239/5/4600.pdf.jpgbd83cdb6f2d7dca5f5a8b16776f5b306MD55ufscar/62392023-09-18 18:31:52.373oai:repositorio.ufscar.br:ufscar/6239Repositório InstitucionalPUBhttps://repositorio.ufscar.br/oai/requestopendoar:43222023-09-18T18:31:52Repositório Institucional da UFSCAR - Universidade Federal de São Carlos (UFSCAR)false |
dc.title.por.fl_str_mv |
Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas |
dc.title.alternative.eng.fl_str_mv |
Syntheses and structural investigations of supramolecular arrays formed by metalloporphyrins and metallophthalocyanines. |
title |
Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas |
spellingShingle |
Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas Melo, Cristiane Cabral de Química inorgânica Síntese Arranjos supramoleculares mistos Metaloporfirinas Metaloftalocianina Clatrato Metallotetraphenylporphyrins Metallophthalocyanines Mixed tetrapirrolic arrays Clathrate CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas |
title_full |
Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas |
title_fullStr |
Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas |
title_full_unstemmed |
Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas |
title_sort |
Síntese e investigações estruturais de arranjos supramoleculares formados por metaloporfirinas e metaloftalocianinas |
author |
Melo, Cristiane Cabral de |
author_facet |
Melo, Cristiane Cabral de |
author_role |
author |
dc.contributor.authorlattes.por.fl_str_mv |
http://lattes.cnpq.br/8702045345660264 |
dc.contributor.author.fl_str_mv |
Melo, Cristiane Cabral de |
dc.contributor.advisor1.fl_str_mv |
Moreira, Wania da Conceição |
dc.contributor.advisor1Lattes.fl_str_mv |
http://genos.cnpq.br:12010/dwlattes/owa/prc_imp_cv_int?f_cod=K4786312J8 |
dc.contributor.authorID.fl_str_mv |
57ae67ce-c899-4ff1-a529-2c9867046339 |
contributor_str_mv |
Moreira, Wania da Conceição |
dc.subject.por.fl_str_mv |
Química inorgânica Síntese Arranjos supramoleculares mistos Metaloporfirinas Metaloftalocianina Clatrato |
topic |
Química inorgânica Síntese Arranjos supramoleculares mistos Metaloporfirinas Metaloftalocianina Clatrato Metallotetraphenylporphyrins Metallophthalocyanines Mixed tetrapirrolic arrays Clathrate CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Metallotetraphenylporphyrins Metallophthalocyanines Mixed tetrapirrolic arrays Clathrate |
dc.subject.cnpq.fl_str_mv |
CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This thesis involves the syntheses and characterization of four heterotriads formed by metallotetraphenylporphyrins (CoTPP and NiTPP) and metallophthalocyanines (CoPc and NiPc) using pyrazine (pz) and trans-1,2-bis(4-pyridyl)ethylene (bpe) as spacer ligands. The following sequences: NiPc(pz)CoTPP(pz)NiPc, NiTPP(pz)CoPc(pz)NiTPP, NiTPP(bpe)CoPc(bpe)NiTPP and CoTPP(bpe)CoPc(bpe)CoTPP were investigated. All triads were analyzed by infrared and ultraviolet-visible spectroscopy and some of them were characterized by elemental analysis, termogravimetry and differential thermal analysis. The infrared and electronic spectra of the triads showed characteristic absorption bands of the two macrocycles. The elemental data are in a good agreement with the proposed stoichiometry of these arrays. The triad NiTPP(pz)CoPc(pz)NiTPP had its stoichiometry confirmed via thermogravimetry and elemental analysis. Besides these results, this thesis also reports the crystal structure of a new pseudopolymorph of cobalt tetraphenylporphyrin (CoTPP) obtained by single-crystal X-ray diffraction. This non-stoichiometric solvate crystallized in the space group Pī with unit cell parameters distinct from the non-solvated CoTPP, which in general, like others metallotetraphenylporphyrins, tends to crystallize in the tetragonal space group I42d. The triclinic and tetragonal forms differ with respect to the conformation adopted by the macrocycle and also in the phenyl orientation. Crystal packing analysis of this pseudopolymorph revealed the presence of infinite channels along the a axis that are filled by dichloromethane solvent molecules, which represents therefore the first clathrate of CoTPP reported in the literature. |
publishDate |
2012 |
dc.date.available.fl_str_mv |
2012-10-17 2016-06-02T20:34:37Z |
dc.date.issued.fl_str_mv |
2012-06-29 |
dc.date.accessioned.fl_str_mv |
2016-06-02T20:34:37Z |
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.citation.fl_str_mv |
MELO, Cristiane Cabral de. Syntheses and structural investigations of supramolecular arrays formed by metalloporphyrins and metallophthalocyanines.. 2012. 113 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2012. |
dc.identifier.uri.fl_str_mv |
https://repositorio.ufscar.br/handle/ufscar/6239 |
identifier_str_mv |
MELO, Cristiane Cabral de. Syntheses and structural investigations of supramolecular arrays formed by metalloporphyrins and metallophthalocyanines.. 2012. 113 f. Tese (Doutorado em Ciências Exatas e da Terra) - Universidade Federal de São Carlos, São Carlos, 2012. |
url |
https://repositorio.ufscar.br/handle/ufscar/6239 |
dc.language.iso.fl_str_mv |
por |
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por |
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89942258-47c3-45f6-8ba5-2f6976d8a328 |
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info:eu-repo/semantics/openAccess |
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openAccess |
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application/pdf |
dc.publisher.none.fl_str_mv |
Universidade Federal de São Carlos |
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Programa de Pós-Graduação em Química - PPGQ |
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UFSCar |
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BR |
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Universidade Federal de São Carlos |
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