Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato
Ano de defesa: | 2010 |
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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
|
Programa de Pós-Graduação: |
Programa de Pós-Graduação em Química
|
Departamento: |
Química
|
País: |
BR
|
Palavras-chave em Português: | |
Área do conhecimento CNPq: | |
Link de acesso: | http://repositorio.ufsm.br/handle/1/4227 |
Resumo: | Compounds involving phosphinates ligands possess the ability to form strong metal-oxygen bonds in the solid state by virtue of the very electronegative O atoms bound to an electropositive P atom. This fact was the inspiration to the search of the synthesis and characterization of a new type of ligand bisphosphinate (O2PCH2(C6H4)CH2PO2), PMPP2-, in intention to increase the dimensionality of metallic polymers, as well to understand the interactions between metal centers with this flexible ligand. In this work ten new compounds with high dimensionality were synthesized and characterized. The ligand 1,4-phenylenebis(methylene) bis(phenylphosphinate), abbreviated to H2PMPP 1, was synthesized. In its crystal structure, molecules are linked by intermolecular hydrogen bonds to form a two-dimensional layered supramolecular structure. The crystal structure of the ammonium salt of this ligand (NH4)2PMPP 2, formed a three dimensional structure by hydrogen bonding interactions. From aqueous solutions of compound 2 with corresponding metal acetates, nitrates or chlorides, five new coordination polymers and three ionic supramolecular compounds were synthesized. The coordination compound tectopoly-[ Ag2(μ8-PMPP)] 3 had a three-dimensional structure and was considered isostructural to compound 2. The hydrothermal reaction of H2PMPP with MnCl2×4H2O produced the two-dimensional (2D) coordination polymer phyllo-poly-[Mn2(μ4- PMPP)(μ2-H2PMPP)] 4. The series of coordination compounds involving alkaline earth metals, phyllo-poly-[(Ba(H2O)3)2(μ-H2O)2(μ4-PMPP)](PMPP)] 5 and the isostructural, phyllo-poly[Sr2(H2O)4.25(μ-H2O)(μ4-PMPP)(μ3-PMPP)]×3H2O 6 and phyllo-poly[Ca2(H2O)3.65(μ-H2O)(μ4-PMPP)(μ3-PMPP)]×3H2O 7. In 5, 6 and 7, complex nets of hydrogen bonds between the coordinated water molecules and the PMPP2 ligands link the 2D layers into the three-dimensional framework structures. The ionic compounds derived from Co2+, [Co(H2O)4(NC5H6)2](PMPP), 9, and ([Co(H2O)6](PMPP))·2H2O, 10·2H2O were obtained from the dissolution of [Co(PMPP)] 8, in a solution of water/pyridine and cold water, respectively. The compound ([Ni(H2O)6](PMPP)·2H2O, 11 is isostructural with the structure of the compound 10×2H2O. The ionic compounds form supramolecular species formed by hydrogen bonds. The reversible structural rearrangement of 5, 6, 7, 10·2H2O and 11 frameworks was studied. This new flexible ligand bis(phosphinates) can lead to the formation of flexible and dynamic frameworks. This so called structural dynamism and at present is regarded as the basis of a new class of practical materials. Compounds 5, 6, 7, 10·2H2O and 11 were dehydrated leading to 5D, 6D, 7D, 11D and 8; rehydration converted them to their original species. However, for compounds 6D, 7D, this behavior is not verified. The investigation of the mechanism of hydration/ rehydration was done using X-ray powder diffraction techniques, thermoanalytical methods and infrared spectroscopy. |
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2013-04-242013-04-242010-07-19SILVA, Rubia Mara Siqueira da. New Compounds with High Dimensionality Containing the Flexible Ligand Bis(phosphinate).. 2010. 204 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010.http://repositorio.ufsm.br/handle/1/4227Compounds involving phosphinates ligands possess the ability to form strong metal-oxygen bonds in the solid state by virtue of the very electronegative O atoms bound to an electropositive P atom. This fact was the inspiration to the search of the synthesis and characterization of a new type of ligand bisphosphinate (O2PCH2(C6H4)CH2PO2), PMPP2-, in intention to increase the dimensionality of metallic polymers, as well to understand the interactions between metal centers with this flexible ligand. In this work ten new compounds with high dimensionality were synthesized and characterized. The ligand 1,4-phenylenebis(methylene) bis(phenylphosphinate), abbreviated to H2PMPP 1, was synthesized. In its crystal structure, molecules are linked by intermolecular hydrogen bonds to form a two-dimensional layered supramolecular structure. The crystal structure of the ammonium salt of this ligand (NH4)2PMPP 2, formed a three dimensional structure by hydrogen bonding interactions. From aqueous solutions of compound 2 with corresponding metal acetates, nitrates or chlorides, five new coordination polymers and three ionic supramolecular compounds were synthesized. The coordination compound tectopoly-[ Ag2(μ8-PMPP)] 3 had a three-dimensional structure and was considered isostructural to compound 2. The hydrothermal reaction of H2PMPP with MnCl2×4H2O produced the two-dimensional (2D) coordination polymer phyllo-poly-[Mn2(μ4- PMPP)(μ2-H2PMPP)] 4. The series of coordination compounds involving alkaline earth metals, phyllo-poly-[(Ba(H2O)3)2(μ-H2O)2(μ4-PMPP)](PMPP)] 5 and the isostructural, phyllo-poly[Sr2(H2O)4.25(μ-H2O)(μ4-PMPP)(μ3-PMPP)]×3H2O 6 and phyllo-poly[Ca2(H2O)3.65(μ-H2O)(μ4-PMPP)(μ3-PMPP)]×3H2O 7. In 5, 6 and 7, complex nets of hydrogen bonds between the coordinated water molecules and the PMPP2 ligands link the 2D layers into the three-dimensional framework structures. The ionic compounds derived from Co2+, [Co(H2O)4(NC5H6)2](PMPP), 9, and ([Co(H2O)6](PMPP))·2H2O, 10·2H2O were obtained from the dissolution of [Co(PMPP)] 8, in a solution of water/pyridine and cold water, respectively. The compound ([Ni(H2O)6](PMPP)·2H2O, 11 is isostructural with the structure of the compound 10×2H2O. The ionic compounds form supramolecular species formed by hydrogen bonds. The reversible structural rearrangement of 5, 6, 7, 10·2H2O and 11 frameworks was studied. This new flexible ligand bis(phosphinates) can lead to the formation of flexible and dynamic frameworks. This so called structural dynamism and at present is regarded as the basis of a new class of practical materials. Compounds 5, 6, 7, 10·2H2O and 11 were dehydrated leading to 5D, 6D, 7D, 11D and 8; rehydration converted them to their original species. However, for compounds 6D, 7D, this behavior is not verified. The investigation of the mechanism of hydration/ rehydration was done using X-ray powder diffraction techniques, thermoanalytical methods and infrared spectroscopy.Compostos envolvendo ligantes fosfinatos formam fortes interações metal oxigênio devido à polaridade da ligação P O; logo; estes ligantes tornam-se ideais na formação de cadeias poliméricas no estado sólido com um grande número de centros metálicos. Este fato levou a investigação da síntese e caracterização de um novo ligante do tipo bisfosfinato (O2PCH2(C6H4)CH2PO2), PMPP2-, no intuito de aumentar a dimensionalidade de polímeros metálicos, bem como compreender as interações entre os centros metálicos e este ligante flexível. Neste trabalho, foram caracterizadas as estruturas cristalinas de dez novos compostos com alta dimensionalidade; sendo eles: o pró-ligante ácido 1,4- (fenilenodimetileno)-bis-(fenilfosfinato), simplificado por H2PMPP 1, o qual apresenta estrutura bidimensional formada por fortes ligações de hidrogênio. O sal de amônio deste pró-ligante (NH4)2PMPP 2, apresentando uma estrutura tridimensional, também formada por ligações de hidrogênio. E a partir da solução aquosa do composto 2 com os respectivos acetatos, nitratos ou cloretos metálicos, foram sintetizados quatro novos polímeros de coordenação, e três sais complexos supramoleculares. O composto de coordenação tecto-poli-[Ag2(μ8-PMPP)] 3, apresenta uma estrutura tridimensional e foi considerado isoestrutural ao composto 2. Ainda deve-se destacar que, devido à alta estabilidade do pró-ligante 1 foi possível a utilização de síntese hidrotermal, para a formação do phyllo-poli-[Mn2(μ4- PMPP)(μ2-H2PMPP)] 4, o qual apresenta uma estrutura polimérica bidimensional. A série de compostos de coordenação envolvendo metais alcalinos terrosos, phyllopoli-[{ Ba(H2O)3}2(μ-H2O)2(μ4-PMPP)](PMPP) 5, e os isoestruturias, phyllo-poli- [Sr2(H2O)4,25(μ-H2O)(μ4-PMPP)(μ3-PMPP)]×3H2O 6 e phyllo-poli-[Ca2(H2O)3,65(μ- H2O)(μ4-PMPP)(μ3-PMPP)]×3H2O 7, formam uma estrutura polimérica bidimensional e através de ligações de hidrogênio ocorre a formação de uma estrutura em três dimensões. Os sais complexos derivados do Co2+, [Co(H2O)4(NC5H6)2]2(PMPP), 9, e {[Co(H2O)6](PMPP)}×2H2O, 10·2H2O, foram obtidos a partir da dissolução de [CoPMPP] 8, em uma solução de água/piridina e água fria, respectivamente. O composto {[Ni(H2O)6](PMPP)}×2H2O, 11, foi considerado isoestrutural ao composto 10·2H2O. Os sais complexos formam espécies supramoleculares que apresentam ligações de hidrogênio. Finalmente, foi desenvolvido um estudo relacionando este novo ligante bis(fosfinato) com propriedades de Dinamismo Estrutural , considerada atualmente, uma área muito promissora de pesquisa em química. Sendo assim, foi feito uma desidratação dos compostos 5, 6, 7, 10·2H2O e 11, que foram convertidos aos seus respectivos desidratados 5D, 6D, 7D, 8 e 11D, e posteriormente submetidos a um ambiente úmido, para possíveis reidratações. Ficou constado que os compostos 5D, 8 e 11D voltam aos seus originais hidratados. Entretanto, para os compostos 6D, 7D, não ocorreu a volta aos compostos originais hidratados. A investigação do processo de hidratação/reidratação foi feito, utilizando as técnicas de difração de raios-X em policristais, análise termogravimétrica e espectroscopia do infravermelho.Coordenação de Aperfeiçoamento de Pessoal de Nível Superiorapplication/pdfporUniversidade Federal de Santa MariaPrograma de Pós-Graduação em QuímicaUFSMBRQuímicaQuímicaQuímica inorgânicaQuímica supramolecularFosfinatos metálicosCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICANovos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinatoNew compounds with high dimensionality containing the flexible ligand bis(phosphinate)info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/doctoralThesisBurrow, Robert Alanhttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4761460Y1Giacomelli, Cristianohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762951A6Squizani, Fatimahttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4789693T7Andrade, Fabiano Molinos dehttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4733966P9Bortoluzzi, Adailton Joãohttp://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4727981D7http://lattes.cnpq.br/1215582603223545Silva, Rubia Mara Siqueira da100600000000400300300300300300300da77a491-2340-4bec-afed-a9ed5dd5092aaf85751a-8851-4caa-874c-7e63b8b3bdd276f4b1a0-03ef-48e6-88aa-6c682d7ea2f46c576d48-34e1-4008-b46b-a68350c55a17621458e5-a190-491b-b3c8-63833b849167b790c99c-a609-48b7-b612-af3c69649bcdinfo:eu-repo/semantics/openAccessreponame:Biblioteca Digital de Teses e Dissertações do UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALSILVA, RUBIA MARA SIQUEIRA DA.pdfapplication/pdf30579177http://repositorio.ufsm.br/bitstream/1/4227/1/SILVA%2c%20RUBIA%20MARA%20SIQUEIRA%20DA.pdf32724554ce8e3dc711ec099fab190891MD51TEXTSILVA, RUBIA MARA SIQUEIRA DA.pdf.txtSILVA, RUBIA MARA SIQUEIRA DA.pdf.txtExtracted texttext/plain298557http://repositorio.ufsm.br/bitstream/1/4227/2/SILVA%2c%20RUBIA%20MARA%20SIQUEIRA%20DA.pdf.txt9ce3c2462cc06f8714918a802bc9b420MD52THUMBNAILSILVA, RUBIA MARA SIQUEIRA DA.pdf.jpgSILVA, RUBIA MARA SIQUEIRA DA.pdf.jpgIM Thumbnailimage/jpeg5779http://repositorio.ufsm.br/bitstream/1/4227/3/SILVA%2c%20RUBIA%20MARA%20SIQUEIRA%20DA.pdf.jpga5bc4ccd4d15b5b3b990f84483e67777MD531/42272022-07-04 12:03:46.956oai:repositorio.ufsm.br:1/4227Biblioteca Digital de Teses e Dissertaçõeshttps://repositorio.ufsm.br/ONGhttps://repositorio.ufsm.br/oai/requestatendimento.sib@ufsm.br||tedebc@gmail.comopendoar:2022-07-04T15:03:46Biblioteca Digital de Teses e Dissertações do UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato |
dc.title.alternative.eng.fl_str_mv |
New compounds with high dimensionality containing the flexible ligand bis(phosphinate) |
title |
Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato |
spellingShingle |
Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato Silva, Rubia Mara Siqueira da Química Química inorgânica Química supramolecular Fosfinatos metálicos CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato |
title_full |
Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato |
title_fullStr |
Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato |
title_full_unstemmed |
Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato |
title_sort |
Novos compostos de alta dimensionalidade envolvendo um ligante fexível bisfosfinato |
author |
Silva, Rubia Mara Siqueira da |
author_facet |
Silva, Rubia Mara Siqueira da |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Burrow, Robert Alan |
dc.contributor.advisor1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4761460Y1 |
dc.contributor.referee1.fl_str_mv |
Giacomelli, Cristiano |
dc.contributor.referee1Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4762951A6 |
dc.contributor.referee2.fl_str_mv |
Squizani, Fatima |
dc.contributor.referee2Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4789693T7 |
dc.contributor.referee3.fl_str_mv |
Andrade, Fabiano Molinos de |
dc.contributor.referee3Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4733966P9 |
dc.contributor.referee4.fl_str_mv |
Bortoluzzi, Adailton João |
dc.contributor.referee4Lattes.fl_str_mv |
http://buscatextual.cnpq.br/buscatextual/visualizacv.do?id=K4727981D7 |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/1215582603223545 |
dc.contributor.author.fl_str_mv |
Silva, Rubia Mara Siqueira da |
contributor_str_mv |
Burrow, Robert Alan Giacomelli, Cristiano Squizani, Fatima Andrade, Fabiano Molinos de Bortoluzzi, Adailton João |
dc.subject.por.fl_str_mv |
Química Química inorgânica Química supramolecular Fosfinatos metálicos |
topic |
Química Química inorgânica Química supramolecular Fosfinatos metálicos CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
Compounds involving phosphinates ligands possess the ability to form strong metal-oxygen bonds in the solid state by virtue of the very electronegative O atoms bound to an electropositive P atom. This fact was the inspiration to the search of the synthesis and characterization of a new type of ligand bisphosphinate (O2PCH2(C6H4)CH2PO2), PMPP2-, in intention to increase the dimensionality of metallic polymers, as well to understand the interactions between metal centers with this flexible ligand. In this work ten new compounds with high dimensionality were synthesized and characterized. The ligand 1,4-phenylenebis(methylene) bis(phenylphosphinate), abbreviated to H2PMPP 1, was synthesized. In its crystal structure, molecules are linked by intermolecular hydrogen bonds to form a two-dimensional layered supramolecular structure. The crystal structure of the ammonium salt of this ligand (NH4)2PMPP 2, formed a three dimensional structure by hydrogen bonding interactions. From aqueous solutions of compound 2 with corresponding metal acetates, nitrates or chlorides, five new coordination polymers and three ionic supramolecular compounds were synthesized. The coordination compound tectopoly-[ Ag2(μ8-PMPP)] 3 had a three-dimensional structure and was considered isostructural to compound 2. The hydrothermal reaction of H2PMPP with MnCl2×4H2O produced the two-dimensional (2D) coordination polymer phyllo-poly-[Mn2(μ4- PMPP)(μ2-H2PMPP)] 4. The series of coordination compounds involving alkaline earth metals, phyllo-poly-[(Ba(H2O)3)2(μ-H2O)2(μ4-PMPP)](PMPP)] 5 and the isostructural, phyllo-poly[Sr2(H2O)4.25(μ-H2O)(μ4-PMPP)(μ3-PMPP)]×3H2O 6 and phyllo-poly[Ca2(H2O)3.65(μ-H2O)(μ4-PMPP)(μ3-PMPP)]×3H2O 7. In 5, 6 and 7, complex nets of hydrogen bonds between the coordinated water molecules and the PMPP2 ligands link the 2D layers into the three-dimensional framework structures. The ionic compounds derived from Co2+, [Co(H2O)4(NC5H6)2](PMPP), 9, and ([Co(H2O)6](PMPP))·2H2O, 10·2H2O were obtained from the dissolution of [Co(PMPP)] 8, in a solution of water/pyridine and cold water, respectively. The compound ([Ni(H2O)6](PMPP)·2H2O, 11 is isostructural with the structure of the compound 10×2H2O. The ionic compounds form supramolecular species formed by hydrogen bonds. The reversible structural rearrangement of 5, 6, 7, 10·2H2O and 11 frameworks was studied. This new flexible ligand bis(phosphinates) can lead to the formation of flexible and dynamic frameworks. This so called structural dynamism and at present is regarded as the basis of a new class of practical materials. Compounds 5, 6, 7, 10·2H2O and 11 were dehydrated leading to 5D, 6D, 7D, 11D and 8; rehydration converted them to their original species. However, for compounds 6D, 7D, this behavior is not verified. The investigation of the mechanism of hydration/ rehydration was done using X-ray powder diffraction techniques, thermoanalytical methods and infrared spectroscopy. |
publishDate |
2010 |
dc.date.issued.fl_str_mv |
2010-07-19 |
dc.date.accessioned.fl_str_mv |
2013-04-24 |
dc.date.available.fl_str_mv |
2013-04-24 |
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 |
SILVA, Rubia Mara Siqueira da. New Compounds with High Dimensionality Containing the Flexible Ligand Bis(phosphinate).. 2010. 204 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010. |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/4227 |
identifier_str_mv |
SILVA, Rubia Mara Siqueira da. New Compounds with High Dimensionality Containing the Flexible Ligand Bis(phosphinate).. 2010. 204 f. Tese (Doutorado em Química) - Universidade Federal de Santa Maria, Santa Maria, 2010. |
url |
http://repositorio.ufsm.br/handle/1/4227 |
dc.language.iso.fl_str_mv |
por |
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por |
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100600000000 |
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openAccess |
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Universidade Federal de Santa Maria |
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Programa de Pós-Graduação em Química |
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UFSM |
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BR |
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Química |
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Universidade Federal de Santa Maria |
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