η5-Monocyclopenta¬dienylmetal(II) complexes with thienyl acetylide chromophores: synthesis, electrochemical studies and first hyperpolarizabilities
Autor(a) principal: | |
---|---|
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/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. |
id |
RCAP_202e993703f3f0c3f862e84ecc75583b |
---|---|
oai_identifier_str |
oai:dspace.uevora.pt:10174/12474 |
network_acronym_str |
RCAP |
network_name_str |
Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
repository_id_str |
7160 |
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 |
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 |
|
_version_ |
1799136543932153856 |