Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters
Autor(a) principal: | |
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Data de Publicação: | 2009 |
Outros Autores: | , , , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
Texto Completo: | http://hdl.handle.net/10773/6221 |
Resumo: | Three-dimensional lanthanide-organic frameworks formulated as (CH3)2NH2[Ln(pydc)2] · 1/2H2O [Ln3+ ) Eu3+ (1a) or Er3+ (1b); pydc2- corresponds to the diprotonated residue of 2,5-pyridinedicarboxylic acid (H2pydc)], [Er4(OH)4(pydc)4(H2O)3] ·H2O (2), and [PrIII 2PrIV 1.25O(OH)3(pydc)3] (3) have been isolated from typical solvothermal (1a and 1b in N,N-dimethylformamide - DMF) and hydrothermal (2 and 3) syntheses. Materials were characterized in the solid state using single-crystal X-ray diffraction, thermogravimetric analysis, vibrational spectroscopy (FT-IR and FT-Raman), electron microscopy, and CHN elemental analysis. While synthesis in DMF promotes the formation of centrosymmetric dimeric units, which act as building blocks in the construction of anionic ∞ 3{[Ln(pydc)2]-} frameworks having the channels filled by the charge-balancing (CH3)2NH2 + cations generated in situ by the solvolysis of DMF, the use of water as the solvent medium promotes clustering of the lanthanide centers: structures of 2 and 3 contain instead tetrameric [Er4(μ3-OH)4]8+ and hexameric |Pr6(μ3-O)2(μ3-OH)6| clusters which act as the building blocks of the networks, and are bridged by the H2-xpydcx- residues. It is demonstrated that this modular approach is reflected in the topological nature of the materials inducing 4-, 8-, and 14-connected uninodal networks (the nodes being the centers of gravity of the clusters) with topologies identical to those of diamond (family 1), and framework types bct (for 2) and bcu-x (for 3), respectively. The thermogravimetric studies of compound 3 further reveal a significant weight increase between ambient temperature and 450 °C with this being correlated with the uptake of oxygen from the surrounding environment by the praseodymium oxide inorganic core. |
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Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clustersThree-dimensional lanthanide-organic frameworks formulated as (CH3)2NH2[Ln(pydc)2] · 1/2H2O [Ln3+ ) Eu3+ (1a) or Er3+ (1b); pydc2- corresponds to the diprotonated residue of 2,5-pyridinedicarboxylic acid (H2pydc)], [Er4(OH)4(pydc)4(H2O)3] ·H2O (2), and [PrIII 2PrIV 1.25O(OH)3(pydc)3] (3) have been isolated from typical solvothermal (1a and 1b in N,N-dimethylformamide - DMF) and hydrothermal (2 and 3) syntheses. Materials were characterized in the solid state using single-crystal X-ray diffraction, thermogravimetric analysis, vibrational spectroscopy (FT-IR and FT-Raman), electron microscopy, and CHN elemental analysis. While synthesis in DMF promotes the formation of centrosymmetric dimeric units, which act as building blocks in the construction of anionic ∞ 3{[Ln(pydc)2]-} frameworks having the channels filled by the charge-balancing (CH3)2NH2 + cations generated in situ by the solvolysis of DMF, the use of water as the solvent medium promotes clustering of the lanthanide centers: structures of 2 and 3 contain instead tetrameric [Er4(μ3-OH)4]8+ and hexameric |Pr6(μ3-O)2(μ3-OH)6| clusters which act as the building blocks of the networks, and are bridged by the H2-xpydcx- residues. It is demonstrated that this modular approach is reflected in the topological nature of the materials inducing 4-, 8-, and 14-connected uninodal networks (the nodes being the centers of gravity of the clusters) with topologies identical to those of diamond (family 1), and framework types bct (for 2) and bcu-x (for 3), respectively. The thermogravimetric studies of compound 3 further reveal a significant weight increase between ambient temperature and 450 °C with this being correlated with the uptake of oxygen from the surrounding environment by the praseodymium oxide inorganic core.American Chemical Society2012-02-10T15:40:47Z2009-01-01T00:00:00Z2009info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10773/6221eng1528-748310.1021/cg8004932Shi, Fa-NianCunha-Silva, LuisTrindade, TitoPaz, Filipe A. AlmeidaRocha, Joaoinfo:eu-repo/semantics/openAccessreponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãoinstacron:RCAAP2024-02-22T11:06:30Zoai:ria.ua.pt:10773/6221Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T02:42:55.712211Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informaçãofalse |
dc.title.none.fl_str_mv |
Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters |
title |
Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters |
spellingShingle |
Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters Shi, Fa-Nian |
title_short |
Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters |
title_full |
Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters |
title_fullStr |
Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters |
title_full_unstemmed |
Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters |
title_sort |
Three-dimensional lanthanide-organic frameworks based on di-, tetra-, and hexameric clusters |
author |
Shi, Fa-Nian |
author_facet |
Shi, Fa-Nian Cunha-Silva, Luis Trindade, Tito Paz, Filipe A. Almeida Rocha, Joao |
author_role |
author |
author2 |
Cunha-Silva, Luis Trindade, Tito Paz, Filipe A. Almeida Rocha, Joao |
author2_role |
author author author author |
dc.contributor.author.fl_str_mv |
Shi, Fa-Nian Cunha-Silva, Luis Trindade, Tito Paz, Filipe A. Almeida Rocha, Joao |
description |
Three-dimensional lanthanide-organic frameworks formulated as (CH3)2NH2[Ln(pydc)2] · 1/2H2O [Ln3+ ) Eu3+ (1a) or Er3+ (1b); pydc2- corresponds to the diprotonated residue of 2,5-pyridinedicarboxylic acid (H2pydc)], [Er4(OH)4(pydc)4(H2O)3] ·H2O (2), and [PrIII 2PrIV 1.25O(OH)3(pydc)3] (3) have been isolated from typical solvothermal (1a and 1b in N,N-dimethylformamide - DMF) and hydrothermal (2 and 3) syntheses. Materials were characterized in the solid state using single-crystal X-ray diffraction, thermogravimetric analysis, vibrational spectroscopy (FT-IR and FT-Raman), electron microscopy, and CHN elemental analysis. While synthesis in DMF promotes the formation of centrosymmetric dimeric units, which act as building blocks in the construction of anionic ∞ 3{[Ln(pydc)2]-} frameworks having the channels filled by the charge-balancing (CH3)2NH2 + cations generated in situ by the solvolysis of DMF, the use of water as the solvent medium promotes clustering of the lanthanide centers: structures of 2 and 3 contain instead tetrameric [Er4(μ3-OH)4]8+ and hexameric |Pr6(μ3-O)2(μ3-OH)6| clusters which act as the building blocks of the networks, and are bridged by the H2-xpydcx- residues. It is demonstrated that this modular approach is reflected in the topological nature of the materials inducing 4-, 8-, and 14-connected uninodal networks (the nodes being the centers of gravity of the clusters) with topologies identical to those of diamond (family 1), and framework types bct (for 2) and bcu-x (for 3), respectively. The thermogravimetric studies of compound 3 further reveal a significant weight increase between ambient temperature and 450 °C with this being correlated with the uptake of oxygen from the surrounding environment by the praseodymium oxide inorganic core. |
publishDate |
2009 |
dc.date.none.fl_str_mv |
2009-01-01T00:00:00Z 2009 2012-02-10T15:40:47Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://hdl.handle.net/10773/6221 |
url |
http://hdl.handle.net/10773/6221 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
1528-7483 10.1021/cg8004932 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
American Chemical Society |
publisher.none.fl_str_mv |
American Chemical Society |
dc.source.none.fl_str_mv |
reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) instname:Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação instacron:RCAAP |
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Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
instacron_str |
RCAAP |
institution |
RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository.name.fl_str_mv |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799137478094880768 |