Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias
Ano de defesa: | 2018 |
---|---|
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/1/15554 |
Resumo: | This work presents the synthesis and characterization of twenty-six compounds divided into two main groups. The first one approaches compounds containing the oxidorhenium(V) {ReO}3+ moeity and the ligands benzoyl(N,N-diethylthiourea) and isophthaloylbis(N,N-diethylthiourea) in single exchange reactions with triorganylsilanols (Me3SiOH and Ph3SiOH). The complexes synthesized from the precursor (nBu4N)[ReVOCl4] with BzHtuEt2 ligand lead to the formation of discrete molecules where the silanolato ligands are in the trans configuration to the oxido ligand. In contrast, the binuclear complexes formed with bipodal ligand isoph(HtuEt2)2 lead to the formation of two distinguished complexes. In the structure containing the trimethylsilanolato the syn isomer occurs, whereas the use of the bulky ligand triphenylsilanolato leads to formation of the anti isomer due to its steric effect. On the other hand, the second group involves the metallo-supramolecular compounds prepared from the coordination of the ligand 2,5-furanoylbis(N,N-diethylthiourea) with manganese(II), zinc(II) and indium(III). The manganese(II) atom is the most versatile for the construction of both [Mn2(L1)2] and [Mn2(L1)3]2- systems, which are used as hosts for different cations (Na+, K+, Rb+, Cs+, Tl+, Sr2+ and Ba2+). The structures of the metallacoronands [Mn2(L1)2] demonstrate the influence of the solvent in which the compounds are crystallized. The compound containing a DMSO molecule coordinated to the metal centers forms a discrete binuclear complex, while the one containing MeOH molecules as a coligand forms a one-dimensional pseudopolymer due to intermolecular hydrogen bonds. The inclusion of the Na+, Rb+, Cs+ and Tl+ ions in the prior structures in the presence of the acetate anion leads to the formation of the metallacoronates {M Ì [Mn2(L1)2]}(OAc)}n, which are organized as coordination polymers with unidimensional growth, where the acetates act as a bridge ligand between the units. It is not possible to obtain this type of structure with the K+ ion due to the formation of the metalacriptate (Et3NH){K Ì [Mn2(L1)2]}3, considering the template effect that the potassium cation exerts on these structures independent of the stoichiometry used. Complexes with three aroylbistioureas have also been obtained, in which the H3O+, Rb+, Sr2+ and Ba2+ ions are encapsulated. The reactions of the ligand H2L1 with zinc(II) acetate and Na+, K+ or Cs+ ions leads to the formation of three metallacoronates with different topologies. From the use of a trivalent metal such as indium(III) it’s possible to construct metallacrylates [In2(L)3] with the ligands H2L1 and 2,5- thiophenedicarbonylbis(N,N-diethylthiourea) (H2L2), which has a sulfur as the heteroatom in the spacer group. The inclusion of NH4 + and K+ ions in {M Ì [In2(L1)2]}3} systems is identified only in the ligand containing the furan spacer group. Mixed metal complexes are also identified when the metals used can be distinguished by the ligands in systems {K Ì [MnIIMIII(L1)2]}3. The compounds were suitably characterized by single crystal X-ray diffraction, as well as complementary analyzes such as elemental analysis, infrared spectroscopy, high resolution mass spectrometry and nuclear magnetic resonance spectroscopy when appropriate. |
id |
UFSM_21845b2253877a50a2bd4ebe8b1d84a1 |
---|---|
oai_identifier_str |
oai:repositorio.ufsm.br:1/15554 |
network_acronym_str |
UFSM |
network_name_str |
Biblioteca Digital de Teses e Dissertações do UFSM |
repository_id_str |
|
spelling |
2019-02-05T12:47:06Z2019-02-05T12:47:06Z2018-08-03http://repositorio.ufsm.br/handle/1/15554This work presents the synthesis and characterization of twenty-six compounds divided into two main groups. The first one approaches compounds containing the oxidorhenium(V) {ReO}3+ moeity and the ligands benzoyl(N,N-diethylthiourea) and isophthaloylbis(N,N-diethylthiourea) in single exchange reactions with triorganylsilanols (Me3SiOH and Ph3SiOH). The complexes synthesized from the precursor (nBu4N)[ReVOCl4] with BzHtuEt2 ligand lead to the formation of discrete molecules where the silanolato ligands are in the trans configuration to the oxido ligand. In contrast, the binuclear complexes formed with bipodal ligand isoph(HtuEt2)2 lead to the formation of two distinguished complexes. In the structure containing the trimethylsilanolato the syn isomer occurs, whereas the use of the bulky ligand triphenylsilanolato leads to formation of the anti isomer due to its steric effect. On the other hand, the second group involves the metallo-supramolecular compounds prepared from the coordination of the ligand 2,5-furanoylbis(N,N-diethylthiourea) with manganese(II), zinc(II) and indium(III). The manganese(II) atom is the most versatile for the construction of both [Mn2(L1)2] and [Mn2(L1)3]2- systems, which are used as hosts for different cations (Na+, K+, Rb+, Cs+, Tl+, Sr2+ and Ba2+). The structures of the metallacoronands [Mn2(L1)2] demonstrate the influence of the solvent in which the compounds are crystallized. The compound containing a DMSO molecule coordinated to the metal centers forms a discrete binuclear complex, while the one containing MeOH molecules as a coligand forms a one-dimensional pseudopolymer due to intermolecular hydrogen bonds. The inclusion of the Na+, Rb+, Cs+ and Tl+ ions in the prior structures in the presence of the acetate anion leads to the formation of the metallacoronates {M Ì [Mn2(L1)2]}(OAc)}n, which are organized as coordination polymers with unidimensional growth, where the acetates act as a bridge ligand between the units. It is not possible to obtain this type of structure with the K+ ion due to the formation of the metalacriptate (Et3NH){K Ì [Mn2(L1)2]}3, considering the template effect that the potassium cation exerts on these structures independent of the stoichiometry used. Complexes with three aroylbistioureas have also been obtained, in which the H3O+, Rb+, Sr2+ and Ba2+ ions are encapsulated. The reactions of the ligand H2L1 with zinc(II) acetate and Na+, K+ or Cs+ ions leads to the formation of three metallacoronates with different topologies. From the use of a trivalent metal such as indium(III) it’s possible to construct metallacrylates [In2(L)3] with the ligands H2L1 and 2,5- thiophenedicarbonylbis(N,N-diethylthiourea) (H2L2), which has a sulfur as the heteroatom in the spacer group. The inclusion of NH4 + and K+ ions in {M Ì [In2(L1)2]}3} systems is identified only in the ligand containing the furan spacer group. Mixed metal complexes are also identified when the metals used can be distinguished by the ligands in systems {K Ì [MnIIMIII(L1)2]}3. The compounds were suitably characterized by single crystal X-ray diffraction, as well as complementary analyzes such as elemental analysis, infrared spectroscopy, high resolution mass spectrometry and nuclear magnetic resonance spectroscopy when appropriate.O presente trabalho apresenta a síntese e a caracterização de vinte e seis compostos divididos em dois grupos principais. O primeiro deles aborda os compostos contendo o fragmento óxido-rênio(V) {ReO}3+ e ligantes benzoil(N,N-dietiltioureia) e isoftaloilbis(N,N-dietiltioureia) em reações de simples troca com triorganilsilanóis (Me3SiOH e Ph3SiOH). Os complexos sintetizados a partir do precursor (nBu4N)[ReVOCl4] com o ligante BzHtuEt2 levam a formação de moléculas discretas onde os ligantes silanolatos encontram-se em configuração trans ao ligante óxido. Em contrapartida, os complexos em que foi utilizado o ligante bipodal isoph(HtuEt2)2 formaram complexos binucleares com duas configurações distintas. Na estrutura em que contém o ligante trimetilsilanolato ocorre a formação do isômero syn, enquanto que a utilização do ligante mais volumoso trifenilsilanolato leva a formação do isômero anti devido ao seu efeito estérico. Por outro lado, o segundo grupo envolve os compostos metalo-supramoleculares preparados a partir da coordenação do ligante 2,5-furanoilbis(N,Ndietiltioureia) (H2L1) com manganês(II), zinco(II) e índio(III). O átomo de manganês(II) mostra-se o mais versátil para a construção tanto de sistemas [Mn2(L1)2] quanto [Mn2(L1)3]2-, os quais são utilizados como hospedeiros de diferentes cátions (Na+, K+, Rb+, Cs+, Tl+, Sr2+ e Ba2+). As estruturas dos metalacoronandos [Mn2(L1)2] demonstram a influência do solvente em que o composto é cristalizado. O composto contendo uma molécula DMSO coordenado aos metais forma um complexo dinuclear discreto, enquanto o que contem moléculas de MeOH como coligante forma um pseudopolímero com crescimento unidimensional devido a ligações de hidrogênio intermoleculares. A inclusão dos íons Na+, Rb+, Cs+ e Tl+ nas estruturas anteriores, na presença do ânion acetato, leva a formação dos metalacoronatos {M Ì [Mn2(L1)2]}(OAc)}n, os quais estão organizados na forma de polímeros de coordenação com crescimento unidimensional, onde os ligantes acetatos atuam como ponte entre as unidades. Não é possível a obtenção desse tipo de estrutura com o íon K+ devido a formação do metalacriptato (Et3NH){K Ì [Mn2(L1)2]}3, tendo em vista o efeito template que o cátion potássio exerce nestas estruturas independente da estequiometria utilizada. Complexos com três ligantes também foram obtidos, no qual os íons H3O+, Rb+, Sr2+ e Ba2+ são encapsulados. As reações do ligante H2L1 com acetato de zinco(II) e os íons Na+, K+ ou Cs+ levam a formação de metalocoronatos com diferentes topologias. A partir da utilização de um metal trivalente como índio(III) é possível a construção de metalacriptandos [In2(L)3] com os ligantes H2L1 e 2,5- tiofenodicarbonilbis(N,N-dietiltioureia) (H2L2), o qual possui um enxofre como heteroátomo no grupo espaçador. A inclusão de íons NH4 + e K+ em sistemas do tipo {M Ì [In2(L1)2]}3}+ é identificada somente no ligante contendo o grupo espaçador furano. Complexos mistos também são identificados quando os metais utilizados conseguem ser distinguidos pelos ligantes em sistemas do tipo {K Ì [MnIIMIII(L1)2]}3. Os compostos foram devidamente caracterizados por difração de raios X em monocristal, além de análises complementares como análise elementar, espectroscopia na região do infravermelho, espectrometria de massa de alta resolução e espectroscopia de ressonância magnética nuclear quando apropriado.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESporUniversidade 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/openAccessQuímica de coordenação supramolecularAroilbistioureiaComplexos oligonuclearesPolímeros de coordenaçãoQuímica hospedeiro-convidadoMetais alcalinos e alcalinos terrososSupramolecular coordination chemistryAroylbistioureiasOligonuclear complexesCoordination polymersHost-guest chemistryAlkali and alkaline earth metalsCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICAArquiteturas metalo-supramoleculares em derivados de aroilbistioureiasMetallo-supramolecular architectures on aroylbisthioureas derivativesinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisLang, Ernesto Schulzhttp://lattes.cnpq.br/4481982189769819Pinheiro, Adriana Castrohttp://lattes.cnpq.br/3754600563109353Back, Davi Fernandohttp://lattes.cnpq.br/3778138554788107Nunes, Giovana Gioppohttp://lattes.cnpq.br/1856394278836668Giacomelli, Vanessa Schmidthttp://lattes.cnpq.br/0181326876779784http://lattes.cnpq.br/8747868835422752Wioppiold, Thomaz Arruda1006000000006000c9d7568-d5c4-466d-b807-0125a7d37b973de3d353-c11c-4716-ac61-7afd05cb5cc1d2affe14-de5b-4ab6-afc3-66619292d6f5f33f5bf0-5193-4fac-992b-192381823da8c732cee9-9d53-494d-b62a-4f7d1dfc03a6070561da-7f47-4e71-8a41-6e3759afbf35reponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALTES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdfTES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdfTese de Doutoradoapplication/pdf11199403http://repositorio.ufsm.br/bitstream/1/15554/1/TES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf3aad0a9943fe70bf1085570229a41a0aMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-81956http://repositorio.ufsm.br/bitstream/1/15554/3/license.txt2f0571ecee68693bd5cd3f17c1e075dfMD53CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8805http://repositorio.ufsm.br/bitstream/1/15554/2/license_rdf4460e5956bc1d1639be9ae6146a50347MD52TEXTTES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf.txtTES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf.txtExtracted texttext/plain411685http://repositorio.ufsm.br/bitstream/1/15554/4/TES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf.txta7f997a3fe6da074540fd0f1e49b7779MD54THUMBNAILTES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf.jpgTES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf.jpgIM Thumbnailimage/jpeg4375http://repositorio.ufsm.br/bitstream/1/15554/5/TES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf.jpg5610cadb0b9a7a1f9b9d3784d5167c46MD551/155542019-02-06 03:02:22.739oai:repositorio.ufsm.br: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 Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2019-02-06T05:02:22Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias |
dc.title.alternative.eng.fl_str_mv |
Metallo-supramolecular architectures on aroylbisthioureas derivatives |
title |
Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias |
spellingShingle |
Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias Wioppiold, Thomaz Arruda Química de coordenação supramolecular Aroilbistioureia Complexos oligonucleares Polímeros de coordenação Química hospedeiro-convidado Metais alcalinos e alcalinos terrosos Supramolecular coordination chemistry Aroylbistioureias Oligonuclear complexes Coordination polymers Host-guest chemistry Alkali and alkaline earth metals CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias |
title_full |
Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias |
title_fullStr |
Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias |
title_full_unstemmed |
Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias |
title_sort |
Arquiteturas metalo-supramoleculares em derivados de aroilbistioureias |
author |
Wioppiold, Thomaz Arruda |
author_facet |
Wioppiold, Thomaz Arruda |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Lang, Ernesto Schulz |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/4481982189769819 |
dc.contributor.referee1.fl_str_mv |
Pinheiro, Adriana Castro |
dc.contributor.referee1Lattes.fl_str_mv |
http://lattes.cnpq.br/3754600563109353 |
dc.contributor.referee2.fl_str_mv |
Back, Davi Fernando |
dc.contributor.referee2Lattes.fl_str_mv |
http://lattes.cnpq.br/3778138554788107 |
dc.contributor.referee3.fl_str_mv |
Nunes, Giovana Gioppo |
dc.contributor.referee3Lattes.fl_str_mv |
http://lattes.cnpq.br/1856394278836668 |
dc.contributor.referee4.fl_str_mv |
Giacomelli, Vanessa Schmidt |
dc.contributor.referee4Lattes.fl_str_mv |
http://lattes.cnpq.br/0181326876779784 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/8747868835422752 |
dc.contributor.author.fl_str_mv |
Wioppiold, Thomaz Arruda |
contributor_str_mv |
Lang, Ernesto Schulz Pinheiro, Adriana Castro Back, Davi Fernando Nunes, Giovana Gioppo Giacomelli, Vanessa Schmidt |
dc.subject.por.fl_str_mv |
Química de coordenação supramolecular Aroilbistioureia Complexos oligonucleares Polímeros de coordenação Química hospedeiro-convidado Metais alcalinos e alcalinos terrosos |
topic |
Química de coordenação supramolecular Aroilbistioureia Complexos oligonucleares Polímeros de coordenação Química hospedeiro-convidado Metais alcalinos e alcalinos terrosos Supramolecular coordination chemistry Aroylbistioureias Oligonuclear complexes Coordination polymers Host-guest chemistry Alkali and alkaline earth metals CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Supramolecular coordination chemistry Aroylbistioureias Oligonuclear complexes Coordination polymers Host-guest chemistry Alkali and alkaline earth metals |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work presents the synthesis and characterization of twenty-six compounds divided into two main groups. The first one approaches compounds containing the oxidorhenium(V) {ReO}3+ moeity and the ligands benzoyl(N,N-diethylthiourea) and isophthaloylbis(N,N-diethylthiourea) in single exchange reactions with triorganylsilanols (Me3SiOH and Ph3SiOH). The complexes synthesized from the precursor (nBu4N)[ReVOCl4] with BzHtuEt2 ligand lead to the formation of discrete molecules where the silanolato ligands are in the trans configuration to the oxido ligand. In contrast, the binuclear complexes formed with bipodal ligand isoph(HtuEt2)2 lead to the formation of two distinguished complexes. In the structure containing the trimethylsilanolato the syn isomer occurs, whereas the use of the bulky ligand triphenylsilanolato leads to formation of the anti isomer due to its steric effect. On the other hand, the second group involves the metallo-supramolecular compounds prepared from the coordination of the ligand 2,5-furanoylbis(N,N-diethylthiourea) with manganese(II), zinc(II) and indium(III). The manganese(II) atom is the most versatile for the construction of both [Mn2(L1)2] and [Mn2(L1)3]2- systems, which are used as hosts for different cations (Na+, K+, Rb+, Cs+, Tl+, Sr2+ and Ba2+). The structures of the metallacoronands [Mn2(L1)2] demonstrate the influence of the solvent in which the compounds are crystallized. The compound containing a DMSO molecule coordinated to the metal centers forms a discrete binuclear complex, while the one containing MeOH molecules as a coligand forms a one-dimensional pseudopolymer due to intermolecular hydrogen bonds. The inclusion of the Na+, Rb+, Cs+ and Tl+ ions in the prior structures in the presence of the acetate anion leads to the formation of the metallacoronates {M Ì [Mn2(L1)2]}(OAc)}n, which are organized as coordination polymers with unidimensional growth, where the acetates act as a bridge ligand between the units. It is not possible to obtain this type of structure with the K+ ion due to the formation of the metalacriptate (Et3NH){K Ì [Mn2(L1)2]}3, considering the template effect that the potassium cation exerts on these structures independent of the stoichiometry used. Complexes with three aroylbistioureas have also been obtained, in which the H3O+, Rb+, Sr2+ and Ba2+ ions are encapsulated. The reactions of the ligand H2L1 with zinc(II) acetate and Na+, K+ or Cs+ ions leads to the formation of three metallacoronates with different topologies. From the use of a trivalent metal such as indium(III) it’s possible to construct metallacrylates [In2(L)3] with the ligands H2L1 and 2,5- thiophenedicarbonylbis(N,N-diethylthiourea) (H2L2), which has a sulfur as the heteroatom in the spacer group. The inclusion of NH4 + and K+ ions in {M Ì [In2(L1)2]}3} systems is identified only in the ligand containing the furan spacer group. Mixed metal complexes are also identified when the metals used can be distinguished by the ligands in systems {K Ì [MnIIMIII(L1)2]}3. The compounds were suitably characterized by single crystal X-ray diffraction, as well as complementary analyzes such as elemental analysis, infrared spectroscopy, high resolution mass spectrometry and nuclear magnetic resonance spectroscopy when appropriate. |
publishDate |
2018 |
dc.date.issued.fl_str_mv |
2018-08-03 |
dc.date.accessioned.fl_str_mv |
2019-02-05T12:47:06Z |
dc.date.available.fl_str_mv |
2019-02-05T12:47:06Z |
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/1/15554 |
url |
http://repositorio.ufsm.br/handle/1/15554 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 |
dc.relation.authority.fl_str_mv |
0c9d7568-d5c4-466d-b807-0125a7d37b97 3de3d353-c11c-4716-ac61-7afd05cb5cc1 d2affe14-de5b-4ab6-afc3-66619292d6f5 f33f5bf0-5193-4fac-992b-192381823da8 c732cee9-9d53-494d-b62a-4f7d1dfc03a6 070561da-7f47-4e71-8a41-6e3759afbf35 |
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 |
reponame:Biblioteca Digital de Teses e Dissertações do 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 |
Biblioteca Digital de Teses e Dissertações do UFSM |
collection |
Biblioteca Digital de Teses e Dissertações do UFSM |
bitstream.url.fl_str_mv |
http://repositorio.ufsm.br/bitstream/1/15554/1/TES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf http://repositorio.ufsm.br/bitstream/1/15554/3/license.txt http://repositorio.ufsm.br/bitstream/1/15554/2/license_rdf http://repositorio.ufsm.br/bitstream/1/15554/4/TES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf.txt http://repositorio.ufsm.br/bitstream/1/15554/5/TES_PPGQUIMICA_2018_WIOPPIOLD_THOMAZ.pdf.jpg |
bitstream.checksum.fl_str_mv |
3aad0a9943fe70bf1085570229a41a0a 2f0571ecee68693bd5cd3f17c1e075df 4460e5956bc1d1639be9ae6146a50347 a7f997a3fe6da074540fd0f1e49b7779 5610cadb0b9a7a1f9b9d3784d5167c46 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
atendimento.sib@ufsm.br||tedebc@gmail.com |
_version_ |
1793240148459126784 |