Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin

Detalhes bibliográficos
Autor(a) principal: Melo, J. Seixas de
Data de Publicação: 2005
Outros Autores: Sobral, Abílio J. F. N., Gonsalves, A. M. d'A. Rocha, Burrows, Hugh D.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Científico de Acesso Aberto de Portugal (Repositórios Cientìficos)
Texto Completo: http://hdl.handle.net/10316/5102
https://doi.org/10.1016/j.jphotochem.2004.12.004
Resumo: A bichromophoric system in which anthracene has been covalently linked to meso-tetrakis(phenyl)porphyrin (TPP) moieties by alkylsulfonamide spacers has been synthesized and fully characterized. A spectroscopic and photophysical study of this system in dimethylformamide (DMF) has been undertaken to study electronic energy transfer between the anthracene and porphyrin units in excited singlet and triplet states. By use of steady-state and time-resolved fluorescence techniques as well as phosphorescence and laser flash phototolysis, it is shown that excitation to either the singlet or triplet states of the anthracene leads to energy transfer to the lower lying S1 and T1 states of TPP group. The efficiency and the rate of energy transfer have been determined. Although the estimated efficiency of the energy transfer process in the singlet manifold is high, the coexistence of fluorescence from both moieties when exciting the anthracene, together with observation of a biexponential decay of the porphyrin fluorescence when excited in the porphyrin Soret band suggest that communication exists between the two chromophores. This is discussed in terms of Förster type energy transfer and geminate radical pair mechanisms, possibly involving nonplanar (between chromophores) excited state geometry. In the flash photolysis studies, only the porphyrin triplet state was observed. The dominance of nonradiative deactivation in the overall decay of the excited singlet and triplet states is indicated.
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spelling Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrinPorphyrinsAnthracenePhotophysicsFluorescencePhosphorescenceTriplet stateSinglet stateA bichromophoric system in which anthracene has been covalently linked to meso-tetrakis(phenyl)porphyrin (TPP) moieties by alkylsulfonamide spacers has been synthesized and fully characterized. A spectroscopic and photophysical study of this system in dimethylformamide (DMF) has been undertaken to study electronic energy transfer between the anthracene and porphyrin units in excited singlet and triplet states. By use of steady-state and time-resolved fluorescence techniques as well as phosphorescence and laser flash phototolysis, it is shown that excitation to either the singlet or triplet states of the anthracene leads to energy transfer to the lower lying S1 and T1 states of TPP group. The efficiency and the rate of energy transfer have been determined. Although the estimated efficiency of the energy transfer process in the singlet manifold is high, the coexistence of fluorescence from both moieties when exciting the anthracene, together with observation of a biexponential decay of the porphyrin fluorescence when excited in the porphyrin Soret band suggest that communication exists between the two chromophores. This is discussed in terms of Förster type energy transfer and geminate radical pair mechanisms, possibly involving nonplanar (between chromophores) excited state geometry. In the flash photolysis studies, only the porphyrin triplet state was observed. The dominance of nonradiative deactivation in the overall decay of the excited singlet and triplet states is indicated.http://www.sciencedirect.com/science/article/B6TGY-4F8TKBN-1/1/5c1f57ef1c3195eb7c6546dfa4f427ff2005info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articleaplication/PDFhttp://hdl.handle.net/10316/5102http://hdl.handle.net/10316/5102https://doi.org/10.1016/j.jphotochem.2004.12.004engJournal of Photochemistry and Photobiology A: Chemistry. 172:2 (2005) 151-160Melo, J. Seixas deSobral, Abílio J. F. N.Gonsalves, A. M. d'A. RochaBurrows, Hugh D.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:RCAAP2021-05-25T08:13:28Zoai:estudogeral.uc.pt:10316/5102Portal AgregadorONGhttps://www.rcaap.pt/oai/openaireopendoar:71602024-03-19T21:01:11.455159Repositório 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 Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin
title Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin
spellingShingle Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin
Melo, J. Seixas de
Porphyrins
Anthracene
Photophysics
Fluorescence
Phosphorescence
Triplet state
Singlet state
title_short Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin
title_full Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin
title_fullStr Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin
title_full_unstemmed Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin
title_sort Singlet and triplet energy transfer in a bichromophoric system with anthracene covalently linked through sulfonamide to a meso-tetraphenylporphyrin
author Melo, J. Seixas de
author_facet Melo, J. Seixas de
Sobral, Abílio J. F. N.
Gonsalves, A. M. d'A. Rocha
Burrows, Hugh D.
author_role author
author2 Sobral, Abílio J. F. N.
Gonsalves, A. M. d'A. Rocha
Burrows, Hugh D.
author2_role author
author
author
dc.contributor.author.fl_str_mv Melo, J. Seixas de
Sobral, Abílio J. F. N.
Gonsalves, A. M. d'A. Rocha
Burrows, Hugh D.
dc.subject.por.fl_str_mv Porphyrins
Anthracene
Photophysics
Fluorescence
Phosphorescence
Triplet state
Singlet state
topic Porphyrins
Anthracene
Photophysics
Fluorescence
Phosphorescence
Triplet state
Singlet state
description A bichromophoric system in which anthracene has been covalently linked to meso-tetrakis(phenyl)porphyrin (TPP) moieties by alkylsulfonamide spacers has been synthesized and fully characterized. A spectroscopic and photophysical study of this system in dimethylformamide (DMF) has been undertaken to study electronic energy transfer between the anthracene and porphyrin units in excited singlet and triplet states. By use of steady-state and time-resolved fluorescence techniques as well as phosphorescence and laser flash phototolysis, it is shown that excitation to either the singlet or triplet states of the anthracene leads to energy transfer to the lower lying S1 and T1 states of TPP group. The efficiency and the rate of energy transfer have been determined. Although the estimated efficiency of the energy transfer process in the singlet manifold is high, the coexistence of fluorescence from both moieties when exciting the anthracene, together with observation of a biexponential decay of the porphyrin fluorescence when excited in the porphyrin Soret band suggest that communication exists between the two chromophores. This is discussed in terms of Förster type energy transfer and geminate radical pair mechanisms, possibly involving nonplanar (between chromophores) excited state geometry. In the flash photolysis studies, only the porphyrin triplet state was observed. The dominance of nonradiative deactivation in the overall decay of the excited singlet and triplet states is indicated.
publishDate 2005
dc.date.none.fl_str_mv 2005
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
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dc.identifier.uri.fl_str_mv http://hdl.handle.net/10316/5102
http://hdl.handle.net/10316/5102
https://doi.org/10.1016/j.jphotochem.2004.12.004
url http://hdl.handle.net/10316/5102
https://doi.org/10.1016/j.jphotochem.2004.12.004
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Journal of Photochemistry and Photobiology A: Chemistry. 172:2 (2005) 151-160
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