New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms
In the continuation of our sustained interest in porphyrin-based dendrimers and their use as luminescent photosensitizers for two-photon photodynamic therapy (2P-PDT), we wondered about the effect of changing the connectors in our macromolecular structures. We also wanted to initiate preliminary stu...
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MDPI AG
2023-08-01
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Series: | Photochem |
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Online Access: | https://www.mdpi.com/2673-7256/3/3/21 |
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author | Limiao Shi Zhipeng Sun Nicolas Richy Olivier Mongin Mireille Blanchard-Desce Frédéric Paul Christine O. Paul-Roth |
author_facet | Limiao Shi Zhipeng Sun Nicolas Richy Olivier Mongin Mireille Blanchard-Desce Frédéric Paul Christine O. Paul-Roth |
author_sort | Limiao Shi |
collection | DOAJ |
description | In the continuation of our sustained interest in porphyrin-based dendrimers and their use as luminescent photosensitizers for two-photon photodynamic therapy (2P-PDT), we wondered about the effect of changing the connectors in our macromolecular structures. We also wanted to initiate preliminary studies on <i>meso</i>-tetraarylporphyrins decorated with more electron-releasing arms. Thus, various <i>meso</i>-tetrafluorenylporphyrin-cored star-shaped and dendrimeric derivatives have been synthesized and characterized, as well as their zinc(II) complexes. In the new dendrimeric derivatives, the peripheral fluorenyl units of the dendrons are linked to the inner core either by <i>N-phenylcarbazole</i> (<i>C<sub>Cbz</sub></i>) or <i>triphenylamine</i> (<i>C<sub>Tpa</sub></i>) connectors instead of the more classic <i>1</i>,<i>3</i>,<i>5-phenylene</i> (<i>C<sub>Ph</sub></i>) linkers previously used by us. Selected linear and non-linear optical (LO and NLO) properties were then determined for these compounds via absorption or emission studies and by two-photon excited fluorescence (TPEF) measurements. It was found that the <i>C<sub>C</sub><sub>bz</sub></i>-containing dendrimer, which has the most rigid structure, exhibits a significantly lower two-photon absorption (2PA) cross-section than its <i>C<sub>Tpa</sub></i> analog, presenting a more flexible structure while rather similar luminescence and singlet oxygen activation quantum yields are found for both. The origin of this unexpected discrepancy is briefly discussed based on our photophysical data. It is then demonstrated that the latter dendrimer also outperforms several closely related dendrimers in terms of 2PA action cross-section and 2PA-oxygen sensitization, making its molecular architecture quite appealing for developing new 2PA photosensitizers suited to theranostic uses. |
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spelling | doaj.art-c43de647a8c04886b64375c6f91b7e3b2023-11-19T12:28:56ZengMDPI AGPhotochem2673-72562023-08-013333635910.3390/photochem3030021New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral ArmsLimiao Shi0Zhipeng Sun1Nicolas Richy2Olivier Mongin3Mireille Blanchard-Desce4Frédéric Paul5Christine O. Paul-Roth6Univ. Rennes, INSA Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)—UMR 6226, F-35000 Rennes, FranceUniv. Rennes, INSA Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)—UMR 6226, F-35000 Rennes, FranceUniv. Rennes, INSA Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)—UMR 6226, F-35000 Rennes, FranceUniv. Rennes, INSA Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)—UMR 6226, F-35000 Rennes, FranceUniv. Bordeaux, Institut des Sciences Moléculaires, CNRS UMR 5255), 351 Cours de la Libération, 33405 Talence, FranceUniv. Rennes, INSA Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)—UMR 6226, F-35000 Rennes, FranceUniv. Rennes, INSA Rennes, CNRS, Institut des Sciences Chimiques de Rennes (ISCR)—UMR 6226, F-35000 Rennes, FranceIn the continuation of our sustained interest in porphyrin-based dendrimers and their use as luminescent photosensitizers for two-photon photodynamic therapy (2P-PDT), we wondered about the effect of changing the connectors in our macromolecular structures. We also wanted to initiate preliminary studies on <i>meso</i>-tetraarylporphyrins decorated with more electron-releasing arms. Thus, various <i>meso</i>-tetrafluorenylporphyrin-cored star-shaped and dendrimeric derivatives have been synthesized and characterized, as well as their zinc(II) complexes. In the new dendrimeric derivatives, the peripheral fluorenyl units of the dendrons are linked to the inner core either by <i>N-phenylcarbazole</i> (<i>C<sub>Cbz</sub></i>) or <i>triphenylamine</i> (<i>C<sub>Tpa</sub></i>) connectors instead of the more classic <i>1</i>,<i>3</i>,<i>5-phenylene</i> (<i>C<sub>Ph</sub></i>) linkers previously used by us. Selected linear and non-linear optical (LO and NLO) properties were then determined for these compounds via absorption or emission studies and by two-photon excited fluorescence (TPEF) measurements. It was found that the <i>C<sub>C</sub><sub>bz</sub></i>-containing dendrimer, which has the most rigid structure, exhibits a significantly lower two-photon absorption (2PA) cross-section than its <i>C<sub>Tpa</sub></i> analog, presenting a more flexible structure while rather similar luminescence and singlet oxygen activation quantum yields are found for both. The origin of this unexpected discrepancy is briefly discussed based on our photophysical data. It is then demonstrated that the latter dendrimer also outperforms several closely related dendrimers in terms of 2PA action cross-section and 2PA-oxygen sensitization, making its molecular architecture quite appealing for developing new 2PA photosensitizers suited to theranostic uses.https://www.mdpi.com/2673-7256/3/3/21porphyrinfluorenylphenylcarbazoletriphenylaminetwo-photon absorption |
spellingShingle | Limiao Shi Zhipeng Sun Nicolas Richy Olivier Mongin Mireille Blanchard-Desce Frédéric Paul Christine O. Paul-Roth New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms Photochem porphyrin fluorenyl phenyl carbazole triphenylamine two-photon absorption |
title | New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms |
title_full | New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms |
title_fullStr | New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms |
title_full_unstemmed | New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms |
title_short | New Fluorescent Porphyrins with High Two-Photon Absorption Cross-Sections Designed for Oxygen-Sensitization: Impact of Changing the Connectors in the Peripheral Arms |
title_sort | new fluorescent porphyrins with high two photon absorption cross sections designed for oxygen sensitization impact of changing the connectors in the peripheral arms |
topic | porphyrin fluorenyl phenyl carbazole triphenylamine two-photon absorption |
url | https://www.mdpi.com/2673-7256/3/3/21 |
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