η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities

Detalhes bibliográficos
Autor(a) principal: Mendes, Paulo J.
Data de Publicação: 2014
Outros Autores: Ramalho, J.P. Prates, Carvalho, A. J. Palace, Silva, Tiago J.L., Santos, Ana M., Garcia, M. Helena, Robalo, M. Paula, Büchert, Marina, Wittenburg, Christian, Heck, Jürgen
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10174/12474
Resumo: A series of η5-monocyclopentadienylmetal(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(η5-C5H5)(L)(C≡C{C4H2S}nNO2)] (M=Fe: L= k2-DPPE (n= 1, 2; M=Ru: L= k2-DPPE, 2 PPh3, n= 1, 2; M=Ni: L=PPh3, n= 1, 2) has been synthesized and fully characterized by NMR, FT-IR and UV–Vis spectroscopies. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities () of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push-pull systems is revealed even so several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions besides the main MLCT, clearly control the effectiveness of the organometallic donor ability on the second-order NLO properties of these push-pull systems.
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spelling η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilitiesMonocyclopentadienylmetal complexesthienyl acetylide chromophorescyclic voltammetrynonlinear opticsquadratic hyperpolarizabilitieshyper-Rayleigh scatteringA series of η5-monocyclopentadienylmetal(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(η5-C5H5)(L)(C≡C{C4H2S}nNO2)] (M=Fe: L= k2-DPPE (n= 1, 2; M=Ru: L= k2-DPPE, 2 PPh3, n= 1, 2; M=Ni: L=PPh3, n= 1, 2) has been synthesized and fully characterized by NMR, FT-IR and UV–Vis spectroscopies. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities () of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push-pull systems is revealed even so several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions besides the main MLCT, clearly control the effectiveness of the organometallic donor ability on the second-order NLO properties of these push-pull systems.ACS Publications2015-01-20T18:09:32Z2015-01-202014-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10174/12474http://hdl.handle.net/10174/12474engSilva, T. J. L.; Mendes, P. J.; Santos, A. M.; Garcia, M. H.; Robalo, M. P.; Ramalho, J. P. P.; Carvalho, A. J. P.; Büchert, M.; Wittenburg, C.; Heck, J., Mono(η5-cyclopentadienyl)metal(II) Complexes with Thienyl Acetylide Chromophores: Synthesis, Electrochemical Studies, and First Hyperpolarizabilities, Organometallics 2014, 33 (18), 4655-4671http://pubs.acs.org/doi/abs/10.1021/om4001204QUIpjgm@uevora.ptjpcar@uevora.ptajpalace@uevora.pttjlsilva@gmail.commargaridaggs@gmail.commhgarcia@fc.ul.ptmprobalo@deq.isel.ipl.ptmarina.buechert@chemie.uni-hamburg.dewittenbg@chemie.uni-hamburg.dejuergen.heck@chemie.uni-hamburg.de307Mendes, Paulo J.Ramalho, J.P. PratesCarvalho, A. J. PalaceSilva, Tiago J.L.Santos, Ana M.Garcia, M. HelenaRobalo, M. PaulaBüchert, MarinaWittenburg, ChristianHeck, Jürgeninfo: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:RCAAP2024-01-03T18:56:45Zoai:dspace.uevora.pt:10174/12474Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T01:05:52.768127Repositório 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 η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
title η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
spellingShingle η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
Mendes, Paulo J.
Monocyclopentadienylmetal complexes
thienyl acetylide chromophores
cyclic voltammetry
nonlinear optics
quadratic hyperpolarizabilities
hyper-Rayleigh scattering
title_short η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
title_full η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
title_fullStr η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
title_full_unstemmed η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
title_sort η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
author Mendes, Paulo J.
author_facet Mendes, Paulo J.
Ramalho, J.P. Prates
Carvalho, A. J. Palace
Silva, Tiago J.L.
Santos, Ana M.
Garcia, M. Helena
Robalo, M. Paula
Büchert, Marina
Wittenburg, Christian
Heck, Jürgen
author_role author
author2 Ramalho, J.P. Prates
Carvalho, A. J. Palace
Silva, Tiago J.L.
Santos, Ana M.
Garcia, M. Helena
Robalo, M. Paula
Büchert, Marina
Wittenburg, Christian
Heck, Jürgen
author2_role author
author
author
author
author
author
author
author
author
dc.contributor.author.fl_str_mv Mendes, Paulo J.
Ramalho, J.P. Prates
Carvalho, A. J. Palace
Silva, Tiago J.L.
Santos, Ana M.
Garcia, M. Helena
Robalo, M. Paula
Büchert, Marina
Wittenburg, Christian
Heck, Jürgen
dc.subject.por.fl_str_mv Monocyclopentadienylmetal complexes
thienyl acetylide chromophores
cyclic voltammetry
nonlinear optics
quadratic hyperpolarizabilities
hyper-Rayleigh scattering
topic Monocyclopentadienylmetal complexes
thienyl acetylide chromophores
cyclic voltammetry
nonlinear optics
quadratic hyperpolarizabilities
hyper-Rayleigh scattering
description A series of η5-monocyclopentadienylmetal(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(η5-C5H5)(L)(C≡C{C4H2S}nNO2)] (M=Fe: L= k2-DPPE (n= 1, 2; M=Ru: L= k2-DPPE, 2 PPh3, n= 1, 2; M=Ni: L=PPh3, n= 1, 2) has been synthesized and fully characterized by NMR, FT-IR and UV–Vis spectroscopies. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities () of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push-pull systems is revealed even so several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions besides the main MLCT, clearly control the effectiveness of the organometallic donor ability on the second-order NLO properties of these push-pull systems.
publishDate 2014
dc.date.none.fl_str_mv 2014-01-01T00:00:00Z
2015-01-20T18:09:32Z
2015-01-20
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/10174/12474
http://hdl.handle.net/10174/12474
url http://hdl.handle.net/10174/12474
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Silva, T. J. L.; Mendes, P. J.; Santos, A. M.; Garcia, M. H.; Robalo, M. P.; Ramalho, J. P. P.; Carvalho, A. J. P.; Büchert, M.; Wittenburg, C.; Heck, J., Mono(η5-cyclopentadienyl)metal(II) Complexes with Thienyl Acetylide Chromophores: Synthesis, Electrochemical Studies, and First Hyperpolarizabilities, Organometallics 2014, 33 (18), 4655-4671
http://pubs.acs.org/doi/abs/10.1021/om4001204
QUI
pjgm@uevora.pt
jpcar@uevora.pt
ajpalace@uevora.pt
tjlsilva@gmail.com
margaridaggs@gmail.com
mhgarcia@fc.ul.pt
mprobalo@deq.isel.ipl.pt
marina.buechert@chemie.uni-hamburg.de
wittenbg@chemie.uni-hamburg.de
juergen.heck@chemie.uni-hamburg.de
307
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv ACS Publications
publisher.none.fl_str_mv ACS Publications
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
instname_str Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
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reponame_str Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
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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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