Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands
Autor(a) principal: | |
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Data de Publicação: | 2014 |
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/10316/27130 https://doi.org/10.1016/j.jorganchem.2013.12.028 |
Resumo: | The effect of the phenolate ring derivatisation on the magnetic properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands both in solid state and solution have been investigated. Two new complexes [Fe(3,5-Br-salEen)2]ClO4.EtOH (5) and [Fe(3,5-Br-salEen)2]BPh4.DMF (6) have been synthesised. SQUID magnetometry studies on these complexes showed that while complex 5 is in the low-spin (LS) state, complex 6 displays a gradual and incomplete spin crossover (SCO) transition over the temperature measured. Solution measurements on a series of six complexes – [Fe(salEen)2]ClO4 (1), [Fe(salEen)2]BPh4·0.5H2O (2), [Fe(5-Br-salEen)2]ClO4 (3), [Fe(5-Br-salEen)2]BPh4·DMF (4), [Fe(3,5-Br-salEen)2]ClO4·EtOH (5) and [Fe(3,5-Br-salEen)2]BPh4·DMF (6) – were performed by UV–vis and NMR spectroscopies and cyclic voltammetry. Solution studies show that the presence of electron withdrawing groups (bromine atoms) affect the electronic density at the phenolate ring, thus influencing the ligand field strength and the separation between the t2g and eg* energy levels. The presence of two bromide substituents at the phenolate ring has a more pronounced effect on the magnetic behaviour in solution than in the solid state, with both complexes 5 and 6 adopting preferentially the LS state. Electrochemical studies of complexes 1–6 reveal that the reduction of the metallic centres in the complexes with electron withdrawing groups is easier, with E1/2 values of iron moving to more positive potentials with the number of bromide substituents at the phenolate ring. |
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Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligandsSpin crossoverFe(III) complexesElectron withdrawing groupsEvans methodCyclic voltammetryThe effect of the phenolate ring derivatisation on the magnetic properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands both in solid state and solution have been investigated. Two new complexes [Fe(3,5-Br-salEen)2]ClO4.EtOH (5) and [Fe(3,5-Br-salEen)2]BPh4.DMF (6) have been synthesised. SQUID magnetometry studies on these complexes showed that while complex 5 is in the low-spin (LS) state, complex 6 displays a gradual and incomplete spin crossover (SCO) transition over the temperature measured. Solution measurements on a series of six complexes – [Fe(salEen)2]ClO4 (1), [Fe(salEen)2]BPh4·0.5H2O (2), [Fe(5-Br-salEen)2]ClO4 (3), [Fe(5-Br-salEen)2]BPh4·DMF (4), [Fe(3,5-Br-salEen)2]ClO4·EtOH (5) and [Fe(3,5-Br-salEen)2]BPh4·DMF (6) – were performed by UV–vis and NMR spectroscopies and cyclic voltammetry. Solution studies show that the presence of electron withdrawing groups (bromine atoms) affect the electronic density at the phenolate ring, thus influencing the ligand field strength and the separation between the t2g and eg* energy levels. The presence of two bromide substituents at the phenolate ring has a more pronounced effect on the magnetic behaviour in solution than in the solid state, with both complexes 5 and 6 adopting preferentially the LS state. Electrochemical studies of complexes 1–6 reveal that the reduction of the metallic centres in the complexes with electron withdrawing groups is easier, with E1/2 values of iron moving to more positive potentials with the number of bromide substituents at the phenolate ring.Elsevier2014-06-15info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/27130http://hdl.handle.net/10316/27130https://doi.org/10.1016/j.jorganchem.2013.12.028engMARTINHO, Paulo M. [et al.] - Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands. "Journal of Organometallic Chemistry". ISSN 0022-328X. Vol. 760 (2014) p. 48-540022-328Xhttp://www.sciencedirect.com/science/article/pii/S0022328X13008929Martinho, Paulo N.Vicente, Ana I.Realista, SaraSaraiva, Marta S.Melato, Ana I.Brandão, PaulaFerreira, Liliana P.Carvalho, Maria de Deusinfo: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:RCAAP2020-05-25T12:50:30Zoai:estudogeral.uc.pt:10316/27130Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T20:59:56.154406Repositório 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 |
Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands |
title |
Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands |
spellingShingle |
Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands Martinho, Paulo N. Spin crossover Fe(III) complexes Electron withdrawing groups Evans method Cyclic voltammetry |
title_short |
Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands |
title_full |
Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands |
title_fullStr |
Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands |
title_full_unstemmed |
Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands |
title_sort |
Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands |
author |
Martinho, Paulo N. |
author_facet |
Martinho, Paulo N. Vicente, Ana I. Realista, Sara Saraiva, Marta S. Melato, Ana I. Brandão, Paula Ferreira, Liliana P. Carvalho, Maria de Deus |
author_role |
author |
author2 |
Vicente, Ana I. Realista, Sara Saraiva, Marta S. Melato, Ana I. Brandão, Paula Ferreira, Liliana P. Carvalho, Maria de Deus |
author2_role |
author author author author author author author |
dc.contributor.author.fl_str_mv |
Martinho, Paulo N. Vicente, Ana I. Realista, Sara Saraiva, Marta S. Melato, Ana I. Brandão, Paula Ferreira, Liliana P. Carvalho, Maria de Deus |
dc.subject.por.fl_str_mv |
Spin crossover Fe(III) complexes Electron withdrawing groups Evans method Cyclic voltammetry |
topic |
Spin crossover Fe(III) complexes Electron withdrawing groups Evans method Cyclic voltammetry |
description |
The effect of the phenolate ring derivatisation on the magnetic properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands both in solid state and solution have been investigated. Two new complexes [Fe(3,5-Br-salEen)2]ClO4.EtOH (5) and [Fe(3,5-Br-salEen)2]BPh4.DMF (6) have been synthesised. SQUID magnetometry studies on these complexes showed that while complex 5 is in the low-spin (LS) state, complex 6 displays a gradual and incomplete spin crossover (SCO) transition over the temperature measured. Solution measurements on a series of six complexes – [Fe(salEen)2]ClO4 (1), [Fe(salEen)2]BPh4·0.5H2O (2), [Fe(5-Br-salEen)2]ClO4 (3), [Fe(5-Br-salEen)2]BPh4·DMF (4), [Fe(3,5-Br-salEen)2]ClO4·EtOH (5) and [Fe(3,5-Br-salEen)2]BPh4·DMF (6) – were performed by UV–vis and NMR spectroscopies and cyclic voltammetry. Solution studies show that the presence of electron withdrawing groups (bromine atoms) affect the electronic density at the phenolate ring, thus influencing the ligand field strength and the separation between the t2g and eg* energy levels. The presence of two bromide substituents at the phenolate ring has a more pronounced effect on the magnetic behaviour in solution than in the solid state, with both complexes 5 and 6 adopting preferentially the LS state. Electrochemical studies of complexes 1–6 reveal that the reduction of the metallic centres in the complexes with electron withdrawing groups is easier, with E1/2 values of iron moving to more positive potentials with the number of bromide substituents at the phenolate ring. |
publishDate |
2014 |
dc.date.none.fl_str_mv |
2014-06-15 |
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/10316/27130 http://hdl.handle.net/10316/27130 https://doi.org/10.1016/j.jorganchem.2013.12.028 |
url |
http://hdl.handle.net/10316/27130 https://doi.org/10.1016/j.jorganchem.2013.12.028 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
MARTINHO, Paulo M. [et al.] - Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands. "Journal of Organometallic Chemistry". ISSN 0022-328X. Vol. 760 (2014) p. 48-54 0022-328X http://www.sciencedirect.com/science/article/pii/S0022328X13008929 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Elsevier |
publisher.none.fl_str_mv |
Elsevier |
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 |
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RCAAP |
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RCAAP |
reponame_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
collection |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) - Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação |
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1799133889502904320 |