Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs
Abstract The singlet fission characteristics of aqueous nanoparticles, self‐assembled from ion pairs of tetracene dicarboxylic acid and various amines with or without chirality, are thoroughly investigated. The structure of the ammonium molecule, the counterion, is found to play a decisive role in d...
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Wiley
2024-10-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202405864 |
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| author | Ilias Papadopoulos Joseph Ka‐Ho Hui Masa‐aki Morikawa Yasuhito Kawahara Kenji Kaneko Kiyoshi Miyata Ken Onda Nobuo Kimizuka |
| author_facet | Ilias Papadopoulos Joseph Ka‐Ho Hui Masa‐aki Morikawa Yasuhito Kawahara Kenji Kaneko Kiyoshi Miyata Ken Onda Nobuo Kimizuka |
| author_sort | Ilias Papadopoulos |
| collection | DOAJ |
| description | Abstract The singlet fission characteristics of aqueous nanoparticles, self‐assembled from ion pairs of tetracene dicarboxylic acid and various amines with or without chirality, are thoroughly investigated. The structure of the ammonium molecule, the counterion, is found to play a decisive role in determining the molecular orientation of the ion pairs and its regularity, spectroscopic properties, the strength of the intermolecular coupling between the tetracene chromophores, and the consequent singlet fission process. Using chiral amines has led to the formation of crystalline nanosheets and efficient singlet fission with a triplet quantum yield as high as 133% ±20% and a rate constant of 6.99 × 109 s−1. The chiral ion pairs also provide a separation channel to free triplets with yields as high as 33% ±10%. In contrast, nanoparticles with achiral counterions do not show singlet fission, which gave low or high fluorescence quantum yields depending on the size of the counterions. The racemic ion pair produces a correlated triplet pair intermediate by singlet fission, but no decorrelation into two free triplets is observed, as triplet‐triplet annihilation dominates. The introduction of chirality enables higher control over orientation and singlet fission in self‐assembled chromophores. It provides new design guidelines for singlet fission materials. |
| format | Article |
| id | doaj-art-7ad6ebeb609845a8938e65266cafd2c7 |
| institution | OA Journals |
| issn | 2198-3844 |
| language | English |
| publishDate | 2024-10-01 |
| publisher | Wiley |
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| series | Advanced Science |
| spelling | doaj-art-7ad6ebeb609845a8938e65266cafd2c72025-08-20T02:10:42ZengWileyAdvanced Science2198-38442024-10-011139n/an/a10.1002/advs.202405864Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion PairsIlias Papadopoulos0Joseph Ka‐Ho Hui1Masa‐aki Morikawa2Yasuhito Kawahara3Kenji Kaneko4Kiyoshi Miyata5Ken Onda6Nobuo Kimizuka7Department of Applied Chemistry Graduate School of Engineering Kyushu University 744 Motooka, Nishi‐ku Fukuoka 819‐0395 JapanDepartment of Applied Chemistry Graduate School of Engineering Kyushu University 744 Motooka, Nishi‐ku Fukuoka 819‐0395 JapanDepartment of Applied Chemistry Graduate School of Engineering Kyushu University 744 Motooka, Nishi‐ku Fukuoka 819‐0395 JapanDepartment of Materials Science and Engineering Graduate School of Engineering Kyushu University 744 Motooka, Nishi‐ku Fukuoka 819‐0395 JapanDepartment of Materials Science and Engineering Graduate School of Engineering Kyushu University 744 Motooka, Nishi‐ku Fukuoka 819‐0395 JapanDepartment of Chemistry Faculty of Science Kyushu University 744 Motooka, Nishi‐ku Fukuoka 819‐0395 JapanDepartment of Chemistry Faculty of Science Kyushu University 744 Motooka, Nishi‐ku Fukuoka 819‐0395 JapanDepartment of Applied Chemistry Graduate School of Engineering Kyushu University 744 Motooka, Nishi‐ku Fukuoka 819‐0395 JapanAbstract The singlet fission characteristics of aqueous nanoparticles, self‐assembled from ion pairs of tetracene dicarboxylic acid and various amines with or without chirality, are thoroughly investigated. The structure of the ammonium molecule, the counterion, is found to play a decisive role in determining the molecular orientation of the ion pairs and its regularity, spectroscopic properties, the strength of the intermolecular coupling between the tetracene chromophores, and the consequent singlet fission process. Using chiral amines has led to the formation of crystalline nanosheets and efficient singlet fission with a triplet quantum yield as high as 133% ±20% and a rate constant of 6.99 × 109 s−1. The chiral ion pairs also provide a separation channel to free triplets with yields as high as 33% ±10%. In contrast, nanoparticles with achiral counterions do not show singlet fission, which gave low or high fluorescence quantum yields depending on the size of the counterions. The racemic ion pair produces a correlated triplet pair intermediate by singlet fission, but no decorrelation into two free triplets is observed, as triplet‐triplet annihilation dominates. The introduction of chirality enables higher control over orientation and singlet fission in self‐assembled chromophores. It provides new design guidelines for singlet fission materials.https://doi.org/10.1002/advs.202405864chiralityion pairsphotochemistryself‐assemblysinglet fission |
| spellingShingle | Ilias Papadopoulos Joseph Ka‐Ho Hui Masa‐aki Morikawa Yasuhito Kawahara Kenji Kaneko Kiyoshi Miyata Ken Onda Nobuo Kimizuka Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs Advanced Science chirality ion pairs photochemistry self‐assembly singlet fission |
| title | Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs |
| title_full | Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs |
| title_fullStr | Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs |
| title_full_unstemmed | Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs |
| title_short | Chirality in Singlet Fission: Controlling Singlet Fission in Aqueous Nanoparticles of Tetracenedicarboxylic Acid Ion Pairs |
| title_sort | chirality in singlet fission controlling singlet fission in aqueous nanoparticles of tetracenedicarboxylic acid ion pairs |
| topic | chirality ion pairs photochemistry self‐assembly singlet fission |
| url | https://doi.org/10.1002/advs.202405864 |
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