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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Main Authors: Limiao Shi, Zhipeng Sun, Nicolas Richy, Olivier Mongin, Mireille Blanchard-Desce, Frédéric Paul, Christine O. Paul-Roth
Format: Article
Language:English
Published: MDPI AG 2023-08-01
Series:Photochem
Subjects:
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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