Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals

Detalhes bibliográficos
Autor(a) principal: Mendes, Paulo J
Data de Publicação: 2011
Outros Autores: Ramalho, J.P. Prates, Carvalho, A.J. Palace
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10174/3696
Resumo: The research of nonlinear optical (NLO) materials has grown in the past decades due to the potential application in optical device technology, like data storage, communication and bio-sensing. For obtaining large molecular second order nonlinear optical (SONLO) responses, i.e. large hyperpolarizabilities (β), molecules have to possess typical “push-pull” asymmetric structures. η5- Monocyclopentadienylrutheinum(II) and iron(II) complexes presenting heterocyclic organic chromophores have proven to be promising systems in this field [1,2]. The presence of a transition metal suggests that it is possible to switch the SONLO response of the material by changing its oxidation state, by electrochemical means for example. In this case, two distinct forms would be expected: the “switched on” form, with high β value; and the “switched-off” form, with negligible or substantially lower β. The use of SONLO properties of organotransition metal complexes in view of the molecular switching has attracted a considerable interest [3]. Herein, we show the application of Density Functional Theory (DFT) to the studies of SONLO properties of two organometallic complexes bearing a benzo[c]thiophene organic ligand as active NLO chromophore. In order to evaluate the structure-activity relationships and to obtain a validation of the theoretical approach, three different exchange-correlation functionals were tested and the results were compared to experimental Hyper-Rayleigh Scattering measurements. Redox studies on organometallic complexes and organic ligand were performed for the enlightenment of the changes in the electronic density and hence in the factors involved in SONLO switching properties.
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spelling Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 FunctionalsNLOSwitchingOrganometallicsDFTThe research of nonlinear optical (NLO) materials has grown in the past decades due to the potential application in optical device technology, like data storage, communication and bio-sensing. For obtaining large molecular second order nonlinear optical (SONLO) responses, i.e. large hyperpolarizabilities (β), molecules have to possess typical “push-pull” asymmetric structures. η5- Monocyclopentadienylrutheinum(II) and iron(II) complexes presenting heterocyclic organic chromophores have proven to be promising systems in this field [1,2]. The presence of a transition metal suggests that it is possible to switch the SONLO response of the material by changing its oxidation state, by electrochemical means for example. In this case, two distinct forms would be expected: the “switched on” form, with high β value; and the “switched-off” form, with negligible or substantially lower β. The use of SONLO properties of organotransition metal complexes in view of the molecular switching has attracted a considerable interest [3]. Herein, we show the application of Density Functional Theory (DFT) to the studies of SONLO properties of two organometallic complexes bearing a benzo[c]thiophene organic ligand as active NLO chromophore. In order to evaluate the structure-activity relationships and to obtain a validation of the theoretical approach, three different exchange-correlation functionals were tested and the results were compared to experimental Hyper-Rayleigh Scattering measurements. Redox studies on organometallic complexes and organic ligand were performed for the enlightenment of the changes in the electronic density and hence in the factors involved in SONLO switching properties.Ninth Triennial Congress of the WORLD ASSOCIATION OF THEORETICAL AND COMPUTATIONAL CHEMISTS WATOC 20112012-01-17T15:29:56Z2012-01-172011-01-01T00:00:00Zinfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10174/3696http://hdl.handle.net/10174/3696engNinth Triennial Congress of the WORLD ASSOCIATION OF THEORETICAL AND COMPUTATIONAL CHEMISTS WATOC 2011, Santiago de Compostela, Spain, 17-22 July, 2011, Abstract PII 061http://www.watoc2011.com/index.php/homeQUIpjgm@uevora.ptjpcar@uevora.ptajpalace@uevora.pt305Mendes, Paulo J,Ramalho, J.P. PratesCarvalho, A.J. Palaceinfo: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:RCAAP2024-01-03T18:41:10Zoai:dspace.uevora.pt:10174/3696Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-20T00:59:09.351431Repositório 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 Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals
title Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals
spellingShingle Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals
Mendes, Paulo J,
NLO
Switching
Organometallics
DFT
title_short Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals
title_full Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals
title_fullStr Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals
title_full_unstemmed Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals
title_sort Organometallic Complexes for Non-Linear Optical Switching: DFT Evaluation of the B3LYP, CAM-B3LYP and M06 Functionals
author Mendes, Paulo J,
author_facet Mendes, Paulo J,
Ramalho, J.P. Prates
Carvalho, A.J. Palace
author_role author
author2 Ramalho, J.P. Prates
Carvalho, A.J. Palace
author2_role author
author
dc.contributor.author.fl_str_mv Mendes, Paulo J,
Ramalho, J.P. Prates
Carvalho, A.J. Palace
dc.subject.por.fl_str_mv NLO
Switching
Organometallics
DFT
topic NLO
Switching
Organometallics
DFT
description The research of nonlinear optical (NLO) materials has grown in the past decades due to the potential application in optical device technology, like data storage, communication and bio-sensing. For obtaining large molecular second order nonlinear optical (SONLO) responses, i.e. large hyperpolarizabilities (β), molecules have to possess typical “push-pull” asymmetric structures. η5- Monocyclopentadienylrutheinum(II) and iron(II) complexes presenting heterocyclic organic chromophores have proven to be promising systems in this field [1,2]. The presence of a transition metal suggests that it is possible to switch the SONLO response of the material by changing its oxidation state, by electrochemical means for example. In this case, two distinct forms would be expected: the “switched on” form, with high β value; and the “switched-off” form, with negligible or substantially lower β. The use of SONLO properties of organotransition metal complexes in view of the molecular switching has attracted a considerable interest [3]. Herein, we show the application of Density Functional Theory (DFT) to the studies of SONLO properties of two organometallic complexes bearing a benzo[c]thiophene organic ligand as active NLO chromophore. In order to evaluate the structure-activity relationships and to obtain a validation of the theoretical approach, three different exchange-correlation functionals were tested and the results were compared to experimental Hyper-Rayleigh Scattering measurements. Redox studies on organometallic complexes and organic ligand were performed for the enlightenment of the changes in the electronic density and hence in the factors involved in SONLO switching properties.
publishDate 2011
dc.date.none.fl_str_mv 2011-01-01T00:00:00Z
2012-01-17T15:29:56Z
2012-01-17
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/10174/3696
http://hdl.handle.net/10174/3696
url http://hdl.handle.net/10174/3696
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Ninth Triennial Congress of the WORLD ASSOCIATION OF THEORETICAL AND COMPUTATIONAL CHEMISTS WATOC 2011, Santiago de Compostela, Spain, 17-22 July, 2011, Abstract PII 061
http://www.watoc2011.com/index.php/home
QUI
pjgm@uevora.pt
jpcar@uevora.pt
ajpalace@uevora.pt
305
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Ninth Triennial Congress of the WORLD ASSOCIATION OF THEORETICAL AND COMPUTATIONAL CHEMISTS WATOC 2011
publisher.none.fl_str_mv Ninth Triennial Congress of the WORLD ASSOCIATION OF THEORETICAL AND COMPUTATIONAL CHEMISTS WATOC 2011
dc.source.none.fl_str_mv reponame:Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
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instacron:RCAAP
instname_str Agência para a Sociedade do Conhecimento (UMIC) - FCT - Sociedade da Informação
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institution RCAAP
reponame_str Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
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