A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic Compounds

This paper deals with a series of new unsymmetrically substituted mesoporphyrins: 5-(2-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHO), 5-(3-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHM), 5-(4-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHP), 5-(2-hydrox...

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Main Authors: Anabela Sousa Oliveira, Dumitru Licsandru, Rica Boscencu, Radu Socoteanu, Veronica Nacea, Luis Filipe Vieira Ferreira
Format: Article
Language:English
Published: Wiley 2009-01-01
Series:International Journal of Photoenergy
Online Access:http://dx.doi.org/10.1155/2009/413915
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author Anabela Sousa Oliveira
Dumitru Licsandru
Rica Boscencu
Radu Socoteanu
Veronica Nacea
Luis Filipe Vieira Ferreira
author_facet Anabela Sousa Oliveira
Dumitru Licsandru
Rica Boscencu
Radu Socoteanu
Veronica Nacea
Luis Filipe Vieira Ferreira
author_sort Anabela Sousa Oliveira
collection DOAJ
description This paper deals with a series of new unsymmetrically substituted mesoporphyrins: 5-(2-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHO), 5-(3-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHM), 5-(4-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHP), 5-(2-hydroxyphenyl)-10,15,20-tris-butyl-21,23-H-porphyrin (TBPOHO), and their parent nonsubstituted compounds, respectively, 5,10,15,20-tetrakis-phenyl-21,23-H-porphyrin (TPP) and 5,10,15,20-tetrakis-butyl-21,23-H-porphyrin (TBP). Several photophysical studies were carried out to access the influence of the unsymmetrical substitution at the porphyrinic macrocycle on porthyrin's photophysical properties, especially porthyrin's efficiency as singlet oxygen sensitizers. The quantum yields of singlet oxygen generation were determined in benzene (ΦΔ(TPP) = 0.66 ± 0.05; ΦΔ(TPPOHO) = 0.69 ± 0.04; ΦΔ(TPPOHM) = 0.62 ± 0.04; ΦΔ(TPPOHP) = 0.73 ± 0.03; ΦΔ(TBP) = 0.76 ± 0.03; ΦΔ(TBPOHO) = 0.73 ± 0.02) using the 5,10,15,20-tetraphenyl-21,23-H-porphine (ΦΔ(TPP) = 0.66) and Phenazine (ΦΔ(Phz) = 0.83) as reference compounds. Their fluorescence quantum yields were found to be (Φf(TPPOHO) = 0.10 ± 0.04; Φf(TPPOHM) = 0.09 ± 0.03; Φf(TPPOHP) = 0.13 ± 0.02; Φf(TBP) = 0.08 ± 0.03 and Φf(TBPOHO) = 0.08 ± 0.02 using 5,10,15,20-tetraphenyl-21,23-H-porphine as reference Φf(TPP) = 0.13). Singlet state lifetimes were also determined in the same solvent. All the porphyrins presented very similar fluorescence lifetimes (mean values of τS (with O2, air equilibrated) = 9.6 ± 0.3 nanoseconds and (without O2, argon purged) = 10.1 ± 0.6 nanoseconds, resp.). The phosphorescence emission was found to be negligible for this series of unsymmetrically substituted mesoporphyrins, but an E-type, thermally activated, delayed fluorescence process was proved to occur at room temperature.
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spelling doaj-art-6da6dff132bf40efa83a7e9bcc3d77d02025-08-20T03:33:52ZengWileyInternational Journal of Photoenergy1110-662X1687-529X2009-01-01200910.1155/2009/413915413915A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic CompoundsAnabela Sousa Oliveira0Dumitru Licsandru1Rica Boscencu2Radu Socoteanu3Veronica Nacea4Luis Filipe Vieira Ferreira5Centro de Química-Física Molecular (CQFM) and Instituto de Nanociencias e Nanotecnologias (IN), Instituto Superior Técnico, Universidade Técnica de Lisboa, Avenida Rovisco Pais, 1049-001 Lisbon, PortugalDepartment of Physical Chemistry, Faculty of Chemistry, University of Bucharest, 4-12 Regina Elisabeta Bulevardul, 030018 Bucharest, RomaniaDepartment of Inorganic Chemistry, Faculty of Pharmacy, “Carol Davila” University of Medicine and Pharmacy, Bucharest, 6 Traian Vuia Street, Sector 1, Bucharest, RomaniaInstitute of Physical Chemistry “I.G. Murgulescu” of the Romanian Academy, 202 Spl. Independentei, 060021 Bucharest-12, RomaniaDepartment of Inorganic Chemistry, Faculty of Pharmacy, “Carol Davila” University of Medicine and Pharmacy, Bucharest, 6 Traian Vuia Street, Sector 1, Bucharest, RomaniaCentro de Química-Física Molecular (CQFM) and Instituto de Nanociencias e Nanotecnologias (IN), Instituto Superior Técnico, Universidade Técnica de Lisboa, Avenida Rovisco Pais, 1049-001 Lisbon, PortugalThis paper deals with a series of new unsymmetrically substituted mesoporphyrins: 5-(2-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHO), 5-(3-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHM), 5-(4-hydroxyphenyl)-10,15,20-tris-phenyl-21,23-H-porphyrin (TPPOHP), 5-(2-hydroxyphenyl)-10,15,20-tris-butyl-21,23-H-porphyrin (TBPOHO), and their parent nonsubstituted compounds, respectively, 5,10,15,20-tetrakis-phenyl-21,23-H-porphyrin (TPP) and 5,10,15,20-tetrakis-butyl-21,23-H-porphyrin (TBP). Several photophysical studies were carried out to access the influence of the unsymmetrical substitution at the porphyrinic macrocycle on porthyrin's photophysical properties, especially porthyrin's efficiency as singlet oxygen sensitizers. The quantum yields of singlet oxygen generation were determined in benzene (ΦΔ(TPP) = 0.66 ± 0.05; ΦΔ(TPPOHO) = 0.69 ± 0.04; ΦΔ(TPPOHM) = 0.62 ± 0.04; ΦΔ(TPPOHP) = 0.73 ± 0.03; ΦΔ(TBP) = 0.76 ± 0.03; ΦΔ(TBPOHO) = 0.73 ± 0.02) using the 5,10,15,20-tetraphenyl-21,23-H-porphine (ΦΔ(TPP) = 0.66) and Phenazine (ΦΔ(Phz) = 0.83) as reference compounds. Their fluorescence quantum yields were found to be (Φf(TPPOHO) = 0.10 ± 0.04; Φf(TPPOHM) = 0.09 ± 0.03; Φf(TPPOHP) = 0.13 ± 0.02; Φf(TBP) = 0.08 ± 0.03 and Φf(TBPOHO) = 0.08 ± 0.02 using 5,10,15,20-tetraphenyl-21,23-H-porphine as reference Φf(TPP) = 0.13). Singlet state lifetimes were also determined in the same solvent. All the porphyrins presented very similar fluorescence lifetimes (mean values of τS (with O2, air equilibrated) = 9.6 ± 0.3 nanoseconds and (without O2, argon purged) = 10.1 ± 0.6 nanoseconds, resp.). The phosphorescence emission was found to be negligible for this series of unsymmetrically substituted mesoporphyrins, but an E-type, thermally activated, delayed fluorescence process was proved to occur at room temperature.http://dx.doi.org/10.1155/2009/413915
spellingShingle Anabela Sousa Oliveira
Dumitru Licsandru
Rica Boscencu
Radu Socoteanu
Veronica Nacea
Luis Filipe Vieira Ferreira
A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic Compounds
International Journal of Photoenergy
title A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic Compounds
title_full A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic Compounds
title_fullStr A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic Compounds
title_full_unstemmed A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic Compounds
title_short A Singlet Oxygen Photogeneration and Luminescence Study of Unsymmetrically Substituted Mesoporphyrinic Compounds
title_sort singlet oxygen photogeneration and luminescence study of unsymmetrically substituted mesoporphyrinic compounds
url http://dx.doi.org/10.1155/2009/413915
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