Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active?
Three new tetraphenylethene (TPE) push–pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2 + 2] cycloaddition–retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-05-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/24/10/8715 |
| _version_ | 1797599841228947456 |
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| author | Maxime Roger Yann Bretonnière Yann Trolez Antoine Vacher Imane Arbouch Jérôme Cornil Gautier Félix Julien De Winter Sébastien Richeter Sébastien Clément Philippe Gerbier |
| author_facet | Maxime Roger Yann Bretonnière Yann Trolez Antoine Vacher Imane Arbouch Jérôme Cornil Gautier Félix Julien De Winter Sébastien Richeter Sébastien Clément Philippe Gerbier |
| author_sort | Maxime Roger |
| collection | DOAJ |
| description | Three new tetraphenylethene (TPE) push–pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2 + 2] cycloaddition–retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2,2-tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F<sub>4</sub>-TCNQ) as electron-deficient alkenes. Only the starting TPE-alkyne displayed significant AIE behavior, whereas for TPE-TCNE, a faint effect was observed, and for TPE-TCNQ and TPE-F<sub>4</sub>-TCNQ, no fluorescence was observed in any conditions. The main ICT bands that dominate the UV–Visible absorption spectra underwent a pronounced red-shift beyond the near-infrared (NIR) region for TPE-F<sub>4</sub>-TCNQ. Based on TD-DFT calculations, it was shown that the ICT character shown by the compounds exclusively originated from the clicked moieties independently of the nature of the central molecular platform. Photothermal (PT) studies conducted on both TPE-TCNQ and TPE-F4-TCNQ in the solid state revealed excellent properties, especially for TPE-F4-TCNQ. These results indicated that CA-RE reaction of TCNQ or F<sub>4</sub>-TCNQ with donor-substituted are promising candidates for PT applications. |
| first_indexed | 2024-03-11T03:40:03Z |
| format | Article |
| id | doaj.art-db6cc4c4b98b446c9cdd6a05af15ded1 |
| institution | Directory Open Access Journal |
| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-11T03:40:03Z |
| publishDate | 2023-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | International Journal of Molecular Sciences |
| spelling | doaj.art-db6cc4c4b98b446c9cdd6a05af15ded12023-11-18T01:40:35ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-05-012410871510.3390/ijms24108715Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active?Maxime Roger0Yann Bretonnière1Yann Trolez2Antoine Vacher3Imane Arbouch4Jérôme Cornil5Gautier Félix6Julien De Winter7Sébastien Richeter8Sébastien Clément9Philippe Gerbier10ICGM, CNRS UMR 5253, ENSCM, University of Montpellier, 34293 Montpellier, FranceENS de Lyon, CNRS UMR 5182, Laboratoire de Chimie, University of Lyon, 69364 Lyon, FranceEcole Nationale Supérieure de Chimie de Rennes, CNRS, ISCR—UMR 6226, University of Rennes, 35065 Rennes, FranceEcole Nationale Supérieure de Chimie de Rennes, CNRS, ISCR—UMR 6226, University of Rennes, 35065 Rennes, FranceLaboratory for Chemistry of Novel Materials, University of Mons-UMONS, 7000 Mons, BelgiumLaboratory for Chemistry of Novel Materials, University of Mons-UMONS, 7000 Mons, BelgiumICGM, CNRS UMR 5253, ENSCM, University of Montpellier, 34293 Montpellier, FranceOrganic Synthesis and Mass Spectrometry Laboratory (S2MOs), University of Mons-UMONS, 7000 Mons, BelgiumICGM, CNRS UMR 5253, ENSCM, University of Montpellier, 34293 Montpellier, FranceICGM, CNRS UMR 5253, ENSCM, University of Montpellier, 34293 Montpellier, FranceICGM, CNRS UMR 5253, ENSCM, University of Montpellier, 34293 Montpellier, FranceThree new tetraphenylethene (TPE) push–pull chromophores exhibiting strong intramolecular charge transfer (ICT) are described. They were obtained via [2 + 2] cycloaddition–retroelectrocyclization (CA-RE) click reactions on an electron-rich alkyne-tetrafunctionalized TPE (TPE-alkyne) using both 1,1,2,2-tetracyanoethene (TCNE), 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F<sub>4</sub>-TCNQ) as electron-deficient alkenes. Only the starting TPE-alkyne displayed significant AIE behavior, whereas for TPE-TCNE, a faint effect was observed, and for TPE-TCNQ and TPE-F<sub>4</sub>-TCNQ, no fluorescence was observed in any conditions. The main ICT bands that dominate the UV–Visible absorption spectra underwent a pronounced red-shift beyond the near-infrared (NIR) region for TPE-F<sub>4</sub>-TCNQ. Based on TD-DFT calculations, it was shown that the ICT character shown by the compounds exclusively originated from the clicked moieties independently of the nature of the central molecular platform. Photothermal (PT) studies conducted on both TPE-TCNQ and TPE-F4-TCNQ in the solid state revealed excellent properties, especially for TPE-F4-TCNQ. These results indicated that CA-RE reaction of TCNQ or F<sub>4</sub>-TCNQ with donor-substituted are promising candidates for PT applications.https://www.mdpi.com/1422-0067/24/10/8715TPEAIEgencycloaddition-retroelectrocyclizationclick chemistryphotothermal applications |
| spellingShingle | Maxime Roger Yann Bretonnière Yann Trolez Antoine Vacher Imane Arbouch Jérôme Cornil Gautier Félix Julien De Winter Sébastien Richeter Sébastien Clément Philippe Gerbier Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active? International Journal of Molecular Sciences TPE AIEgen cycloaddition-retroelectrocyclization click chemistry photothermal applications |
| title | Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active? |
| title_full | Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active? |
| title_fullStr | Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active? |
| title_full_unstemmed | Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active? |
| title_short | Synthesis and Characterization of Tetraphenylethene AIEgen-Based Push–Pull Chromophores for Photothermal Applications: Could the Cycloaddition–Retroelectrocyclization Click Reaction Make Any Molecule Photothermally Active? |
| title_sort | synthesis and characterization of tetraphenylethene aiegen based push pull chromophores for photothermal applications could the cycloaddition retroelectrocyclization click reaction make any molecule photothermally active |
| topic | TPE AIEgen cycloaddition-retroelectrocyclization click chemistry photothermal applications |
| url | https://www.mdpi.com/1422-0067/24/10/8715 |
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