Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State
Autor(a) principal: | |
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Data de Publicação: | 2001 |
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/10316/10641 https://doi.org/10.1021/jp012390x |
Resumo: | The effect of solvent polarity and external heavy atom on the steady state and time-resolved fluorescence properties of the locally excited (LE) state of p-(dimethylamino)benzethyne (DMABE) has been studied. It has been observed that in less polar environments, intersystem crossing (ISC) is the main nonradiative channel of deactivation for the excited species. However, at higher solvent polarity (ET(30) ≥ 44) the activation barrier dependent intramolecular charge transfer (ICT) reaction is the main nonradiative process dominating over ISC. The results reveal that DMABE undergoes an ICT reaction in polar environments to reach a nonfluorescent intramolecular charge transfer (ICT) state. The efficiency of formation of the ICT state of DMABE is compared with that of p-(dimethylamino)benzonitrile (DMABN). The present work settles the controversy raised by two previous works with conflicting results: a theoretical one, predicting that DMABE will undergo ICT reaction even under isolated conditions (Sobolewski, A. L.; Domcke, W. Chem. Phys. Lett. 1996, 259, 119), and an experimental one, excluding the possibility of the ICT process for the same molecular system (Zachariasse, K. A.; Grobys, M.; Tauer, E. Chem. Phys. Lett. 1997, 274, 382). |
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Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT StateThe effect of solvent polarity and external heavy atom on the steady state and time-resolved fluorescence properties of the locally excited (LE) state of p-(dimethylamino)benzethyne (DMABE) has been studied. It has been observed that in less polar environments, intersystem crossing (ISC) is the main nonradiative channel of deactivation for the excited species. However, at higher solvent polarity (ET(30) ≥ 44) the activation barrier dependent intramolecular charge transfer (ICT) reaction is the main nonradiative process dominating over ISC. The results reveal that DMABE undergoes an ICT reaction in polar environments to reach a nonfluorescent intramolecular charge transfer (ICT) state. The efficiency of formation of the ICT state of DMABE is compared with that of p-(dimethylamino)benzonitrile (DMABN). The present work settles the controversy raised by two previous works with conflicting results: a theoretical one, predicting that DMABE will undergo ICT reaction even under isolated conditions (Sobolewski, A. L.; Domcke, W. Chem. Phys. Lett. 1996, 259, 119), and an experimental one, excluding the possibility of the ICT process for the same molecular system (Zachariasse, K. A.; Grobys, M.; Tauer, E. Chem. Phys. Lett. 1997, 274, 382).American Chemical Society2001-11-08info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://hdl.handle.net/10316/10641http://hdl.handle.net/10316/10641https://doi.org/10.1021/jp012390xengThe Journal of Physical Chemistry A. 105:44 (2001) 10025-100301089-5639Chattopadhyay, NitinSerpa, CarlosPereira, Mariette M.Melo, J. Seixas deArnaut, Luis G.Formosinho, Sebastião J.info: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:RCAAP2020-03-09T10:29:46Zoai:estudogeral.uc.pt:10316/10641Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:34.336503Repositório 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 |
Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State |
title |
Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State |
spellingShingle |
Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State Chattopadhyay, Nitin |
title_short |
Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State |
title_full |
Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State |
title_fullStr |
Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State |
title_full_unstemmed |
Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State |
title_sort |
Intramolecular Charge Transfer of p-(Dimethylamino)benzethyne: A Case of Nonfluorescent ICT State |
author |
Chattopadhyay, Nitin |
author_facet |
Chattopadhyay, Nitin Serpa, Carlos Pereira, Mariette M. Melo, J. Seixas de Arnaut, Luis G. Formosinho, Sebastião J. |
author_role |
author |
author2 |
Serpa, Carlos Pereira, Mariette M. Melo, J. Seixas de Arnaut, Luis G. Formosinho, Sebastião J. |
author2_role |
author author author author author |
dc.contributor.author.fl_str_mv |
Chattopadhyay, Nitin Serpa, Carlos Pereira, Mariette M. Melo, J. Seixas de Arnaut, Luis G. Formosinho, Sebastião J. |
description |
The effect of solvent polarity and external heavy atom on the steady state and time-resolved fluorescence properties of the locally excited (LE) state of p-(dimethylamino)benzethyne (DMABE) has been studied. It has been observed that in less polar environments, intersystem crossing (ISC) is the main nonradiative channel of deactivation for the excited species. However, at higher solvent polarity (ET(30) ≥ 44) the activation barrier dependent intramolecular charge transfer (ICT) reaction is the main nonradiative process dominating over ISC. The results reveal that DMABE undergoes an ICT reaction in polar environments to reach a nonfluorescent intramolecular charge transfer (ICT) state. The efficiency of formation of the ICT state of DMABE is compared with that of p-(dimethylamino)benzonitrile (DMABN). The present work settles the controversy raised by two previous works with conflicting results: a theoretical one, predicting that DMABE will undergo ICT reaction even under isolated conditions (Sobolewski, A. L.; Domcke, W. Chem. Phys. Lett. 1996, 259, 119), and an experimental one, excluding the possibility of the ICT process for the same molecular system (Zachariasse, K. A.; Grobys, M.; Tauer, E. Chem. Phys. Lett. 1997, 274, 382). |
publishDate |
2001 |
dc.date.none.fl_str_mv |
2001-11-08 |
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/10316/10641 http://hdl.handle.net/10316/10641 https://doi.org/10.1021/jp012390x |
url |
http://hdl.handle.net/10316/10641 https://doi.org/10.1021/jp012390x |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
The Journal of Physical Chemistry A. 105:44 (2001) 10025-10030 1089-5639 |
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 |
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RCAAP |
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RCAAP |
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Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos) |
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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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1799133906889342976 |