Modulation of Deep-Red to Near-Infrared Room-Temperature Charge-Transfer Phosphorescence of Crystalline "Pyrene Box" Cages by Coupled Ion/Guest Structural Self-Assembly
Organic cocrystals obtained from multicomponent self-assembly have garnered considerable attention due to their distinct phosphorescence properties and broad applications. Yet, there have been limited reports on cocrystal systems that showcase efficient deep-red to near-infrared (NIR) charge-transfer (CT) phosphorescence. Furthermore, effective strategies to modulate the emission pathways of both fluorescence and phosphorescence remain underexplored. In this work, we dedicated our work to four distinct self-assembled cocrystals called "pyrene box" cages using 1,3,6,8-pyrenetetrasulfonate anions (PTS4-), 4-iodoaniline (1), guanidinium (G+), diaminoguanidinium (A2G+), and hydrated K+ countercations. The binding of such cations to PTS4- platforms adaptively modulates their supramolecular stacking self-assembly with guest molecules 1, allowing to steer the fluorescence and phosphorescence pathways. Notably, the confinement of guest molecule 1 within "pyrene box" PTSK{1} and PTSG{1} cages leads to an efficient deep-red to NIR CT phosphorescence emission. The addition of fuming gases like triethylamine and HCl allows reversible pH modulations of guest binding, which in turn induce a reversible transition of the "pyrene box" cage between fluorescence and phosphorescence states. This capability was further illustrated through a proof-of-concept demonstration in shrimp freshness detection. Our findings not only lay a foundation for future supramolecular designs leveraging weak intermolecular host-guest interactions to engineer excited states in interacting chromophores but also broaden the prospective applications of room-temperature phosphorescence materials in food safety detection.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:146 |
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| Enthalten in: |
Journal of the American Chemical Society - 146(2024), 4 vom: 31. Jan., Seite 2484-2493 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Feng, Weixu [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Revised 31.01.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/jacs.3c10206 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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NLM367198118 |
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| 245 | 1 | 0 | |a Modulation of Deep-Red to Near-Infrared Room-Temperature Charge-Transfer Phosphorescence of Crystalline "Pyrene Box" Cages by Coupled Ion/Guest Structural Self-Assembly |
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| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Organic cocrystals obtained from multicomponent self-assembly have garnered considerable attention due to their distinct phosphorescence properties and broad applications. Yet, there have been limited reports on cocrystal systems that showcase efficient deep-red to near-infrared (NIR) charge-transfer (CT) phosphorescence. Furthermore, effective strategies to modulate the emission pathways of both fluorescence and phosphorescence remain underexplored. In this work, we dedicated our work to four distinct self-assembled cocrystals called "pyrene box" cages using 1,3,6,8-pyrenetetrasulfonate anions (PTS4-), 4-iodoaniline (1), guanidinium (G+), diaminoguanidinium (A2G+), and hydrated K+ countercations. The binding of such cations to PTS4- platforms adaptively modulates their supramolecular stacking self-assembly with guest molecules 1, allowing to steer the fluorescence and phosphorescence pathways. Notably, the confinement of guest molecule 1 within "pyrene box" PTSK{1} and PTSG{1} cages leads to an efficient deep-red to NIR CT phosphorescence emission. The addition of fuming gases like triethylamine and HCl allows reversible pH modulations of guest binding, which in turn induce a reversible transition of the "pyrene box" cage between fluorescence and phosphorescence states. This capability was further illustrated through a proof-of-concept demonstration in shrimp freshness detection. Our findings not only lay a foundation for future supramolecular designs leveraging weak intermolecular host-guest interactions to engineer excited states in interacting chromophores but also broaden the prospective applications of room-temperature phosphorescence materials in food safety detection | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Chen, Dong |e verfasserin |4 aut | |
| 700 | 1 | |a Zhao, Yan |e verfasserin |4 aut | |
| 700 | 1 | |a Mu, Bin |e verfasserin |4 aut | |
| 700 | 1 | |a Yan, Hongxia |e verfasserin |4 aut | |
| 700 | 1 | |a Barboiu, Mihail |e verfasserin |4 aut | |
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