A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions
Autor(a) principal: | |
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Data de Publicação: | 2003 |
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/10316/10438 https://doi.org/10.1021/ic034024t |
Resumo: | We report here a structural and photophysical study of lanthanide(III) complexes with the di-deprotonated form of the bibracchial lariat ether N,N‘-bis(2-salicylaldiminobenzyl)-1,10-diaza-15-crown-5. The X-ray crystal structures of [Ce(L2-2H)](ClO4)·0.5H2O (2) and [Sm(L2-2H)](ClO4)·C3H8O (5b) show the metal ion being nine-coordinated and deeply buried in the cavity of the dianionic receptor. Thanks to the formation of a pseudomacrocycle through π−π interaction between one of the phenol rings and one of the benzyl rings, the complexes present a cryptand-like structure in the solid state. 1H and 13C NMR studies on the La(III) complex point that the solid state structure is essentially maintained in acetonitrile solution. High-resolution laser-excited emission spectra of the crystalline Eu(III) complex demonstrate the presence of several coordination sites arising from different conformations of the crown moiety. The ligand-to-Eu(III) energy transfer is relatively efficient at low temperature, but back transfer is implied in the deactivation process, especially at room temperature, because the ligand triplet state lies at very low energy. However, the low energy of the 3ππ* state provides an efficient conversion of the visible light absorbed into near-infrared light emitted by the Nd(III) ion. |
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A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide IonsWe report here a structural and photophysical study of lanthanide(III) complexes with the di-deprotonated form of the bibracchial lariat ether N,N‘-bis(2-salicylaldiminobenzyl)-1,10-diaza-15-crown-5. The X-ray crystal structures of [Ce(L2-2H)](ClO4)·0.5H2O (2) and [Sm(L2-2H)](ClO4)·C3H8O (5b) show the metal ion being nine-coordinated and deeply buried in the cavity of the dianionic receptor. Thanks to the formation of a pseudomacrocycle through π−π interaction between one of the phenol rings and one of the benzyl rings, the complexes present a cryptand-like structure in the solid state. 1H and 13C NMR studies on the La(III) complex point that the solid state structure is essentially maintained in acetonitrile solution. High-resolution laser-excited emission spectra of the crystalline Eu(III) complex demonstrate the presence of several coordination sites arising from different conformations of the crown moiety. The ligand-to-Eu(III) energy transfer is relatively efficient at low temperature, but back transfer is implied in the deactivation process, especially at room temperature, because the ligand triplet state lies at very low energy. However, the low energy of the 3ππ* state provides an efficient conversion of the visible light absorbed into near-infrared light emitted by the Nd(III) ion.American Chemical Society2003-10-20info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/10438http://hdl.handle.net/10316/10438https://doi.org/10.1021/ic034024tengInorganic Chemistry. 42:21 (2003) 6946-69540020-1669González-Lorenzo, MarinaPlatas-Iglesias, CarlosAvecilla, FernandoGeraldes, Carlos F. G. C.Imbert, DanielBünzli, Jean-Claude G.Blas, Andrés deRoinfo: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:RCAAP2020-02-11T18:17:26Zoai:estudogeral.uc.pt:10316/10438Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:55:46.614870Repositório 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 |
A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions |
title |
A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions |
spellingShingle |
A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions González-Lorenzo, Marina |
title_short |
A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions |
title_full |
A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions |
title_fullStr |
A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions |
title_full_unstemmed |
A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions |
title_sort |
A Schiff-Base Bibracchial Lariat Ether Forming a Cryptand-like Cavity for Lanthanide Ions |
author |
González-Lorenzo, Marina |
author_facet |
González-Lorenzo, Marina Platas-Iglesias, Carlos Avecilla, Fernando Geraldes, Carlos F. G. C. Imbert, Daniel Bünzli, Jean-Claude G. Blas, Andrés de Ro |
author_role |
author |
author2 |
Platas-Iglesias, Carlos Avecilla, Fernando Geraldes, Carlos F. G. C. Imbert, Daniel Bünzli, Jean-Claude G. Blas, Andrés de Ro |
author2_role |
author author author author author author author |
dc.contributor.author.fl_str_mv |
González-Lorenzo, Marina Platas-Iglesias, Carlos Avecilla, Fernando Geraldes, Carlos F. G. C. Imbert, Daniel Bünzli, Jean-Claude G. Blas, Andrés de Ro |
description |
We report here a structural and photophysical study of lanthanide(III) complexes with the di-deprotonated form of the bibracchial lariat ether N,N‘-bis(2-salicylaldiminobenzyl)-1,10-diaza-15-crown-5. The X-ray crystal structures of [Ce(L2-2H)](ClO4)·0.5H2O (2) and [Sm(L2-2H)](ClO4)·C3H8O (5b) show the metal ion being nine-coordinated and deeply buried in the cavity of the dianionic receptor. Thanks to the formation of a pseudomacrocycle through π−π interaction between one of the phenol rings and one of the benzyl rings, the complexes present a cryptand-like structure in the solid state. 1H and 13C NMR studies on the La(III) complex point that the solid state structure is essentially maintained in acetonitrile solution. High-resolution laser-excited emission spectra of the crystalline Eu(III) complex demonstrate the presence of several coordination sites arising from different conformations of the crown moiety. The ligand-to-Eu(III) energy transfer is relatively efficient at low temperature, but back transfer is implied in the deactivation process, especially at room temperature, because the ligand triplet state lies at very low energy. However, the low energy of the 3ππ* state provides an efficient conversion of the visible light absorbed into near-infrared light emitted by the Nd(III) ion. |
publishDate |
2003 |
dc.date.none.fl_str_mv |
2003-10-20 |
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/10316/10438 http://hdl.handle.net/10316/10438 https://doi.org/10.1021/ic034024t |
url |
http://hdl.handle.net/10316/10438 https://doi.org/10.1021/ic034024t |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Inorganic Chemistry. 42:21 (2003) 6946-6954 0020-1669 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
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 |
repository.mail.fl_str_mv |
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1799133843876216832 |