Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept, Examples and Applications
Dual-state emissive (DSE) fluorophores are organic dyes displaying fluorescence emission both in dilute and concentrated solution and in the solid-state, as amorphous, single crystal, polycrystalline samples or thin films. This comes in contrast to the vast majority of organic fluorescent dyes which...
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| Format: | Article |
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MDPI AG
2022-04-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/8/2443 |
| _version_ | 1797409866552180736 |
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| author | Timothée Stoerkler Thibault Pariat Adèle D. Laurent Denis Jacquemin Gilles Ulrich Julien Massue |
| author_facet | Timothée Stoerkler Thibault Pariat Adèle D. Laurent Denis Jacquemin Gilles Ulrich Julien Massue |
| author_sort | Timothée Stoerkler |
| collection | DOAJ |
| description | Dual-state emissive (DSE) fluorophores are organic dyes displaying fluorescence emission both in dilute and concentrated solution and in the solid-state, as amorphous, single crystal, polycrystalline samples or thin films. This comes in contrast to the vast majority of organic fluorescent dyes which typically show intense fluorescence in solution but are quenched in concentrated media and in the solid-state owing to π-stacking interactions; a well-known phenomenon called aggregation-caused quenching (ACQ). On the contrary, molecular rotors with a significant number of free rotations have been engineered to show quenched emission in solution but strong fluorescence in the aggregated-state thanks to restriction of the intramolecular motions. This is the concept of aggregation-induced emission (AIE). DSE fluorophores have been far less explored despite the fact that they are at the crossroad of ACQ and AIE phenomena and allow targeting applications both in solution (bio-conjugation, sensing, imaging) and solid-state (organic electronics, data encryption, lasing, luminescent displays). Excited-State Intramolecular Proton Transfer (ESIPT) fluorescence is particularly suitable to engineer DSE dyes. Indeed, ESIPT fluorescence, which relies on a phototautomerism between normal and tautomeric species, is characterized by a strong emission in the solid-state along with a large Stokes’ shift, an enhanced photostability and a strong sensitivity to the close environment, a feature prone to be used in bio-sensing. A drawback that needs to be overcome is their weak emission intensity in solution, owing to detrimental molecular motions in the excited-state. Several strategies have been proposed in that regard. In the past few years, a growing number of examples of DSE-ESIPT dyes have indeed emerged in the literature, enriching the database of such attractive dyes. This review aims at a brief but concise overview on the exploitation of ESIPT luminescence for the optimization of DSE dyes properties. In that perspective, a synergistic approach between organic synthesis, fluorescence spectroscopy and ab initio calculations has proven to be an efficient tool for the construction and optimization of DSE-ESIPT fluorophores. |
| first_indexed | 2024-03-09T04:21:46Z |
| format | Article |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T04:21:46Z |
| publishDate | 2022-04-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj.art-3e36aa33c992417497929ebfa5b981102023-12-03T13:46:12ZengMDPI AGMolecules1420-30492022-04-01278244310.3390/molecules27082443Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept, Examples and ApplicationsTimothée Stoerkler0Thibault Pariat1Adèle D. Laurent2Denis Jacquemin3Gilles Ulrich4Julien Massue5Institut de Chimie et Procédés pour l’Energie, l’Environnement et la Santé (ICPEES), Equipe Chimie Organique pour la Biologie, les Matériaux et l’Optique (COMBO), UMR CNRS 7515, Ecole Européenne de Chimie, Polymères et Matériaux (ECPM), Université de Strasbourg, 25 Rue Becquerel, CEDEX 02, 67087 Strasbourg, FranceInstitut de Chimie et Procédés pour l’Energie, l’Environnement et la Santé (ICPEES), Equipe Chimie Organique pour la Biologie, les Matériaux et l’Optique (COMBO), UMR CNRS 7515, Ecole Européenne de Chimie, Polymères et Matériaux (ECPM), Université de Strasbourg, 25 Rue Becquerel, CEDEX 02, 67087 Strasbourg, FranceChimie et Interdisciplinarités: Synthèse, Analyse et Modélisation (CEISAM), UMR CNRS 6230, Nantes University, 44322 Nantes, FranceChimie et Interdisciplinarités: Synthèse, Analyse et Modélisation (CEISAM), UMR CNRS 6230, Nantes University, 44322 Nantes, FranceInstitut de Chimie et Procédés pour l’Energie, l’Environnement et la Santé (ICPEES), Equipe Chimie Organique pour la Biologie, les Matériaux et l’Optique (COMBO), UMR CNRS 7515, Ecole Européenne de Chimie, Polymères et Matériaux (ECPM), Université de Strasbourg, 25 Rue Becquerel, CEDEX 02, 67087 Strasbourg, FranceInstitut de Chimie et Procédés pour l’Energie, l’Environnement et la Santé (ICPEES), Equipe Chimie Organique pour la Biologie, les Matériaux et l’Optique (COMBO), UMR CNRS 7515, Ecole Européenne de Chimie, Polymères et Matériaux (ECPM), Université de Strasbourg, 25 Rue Becquerel, CEDEX 02, 67087 Strasbourg, FranceDual-state emissive (DSE) fluorophores are organic dyes displaying fluorescence emission both in dilute and concentrated solution and in the solid-state, as amorphous, single crystal, polycrystalline samples or thin films. This comes in contrast to the vast majority of organic fluorescent dyes which typically show intense fluorescence in solution but are quenched in concentrated media and in the solid-state owing to π-stacking interactions; a well-known phenomenon called aggregation-caused quenching (ACQ). On the contrary, molecular rotors with a significant number of free rotations have been engineered to show quenched emission in solution but strong fluorescence in the aggregated-state thanks to restriction of the intramolecular motions. This is the concept of aggregation-induced emission (AIE). DSE fluorophores have been far less explored despite the fact that they are at the crossroad of ACQ and AIE phenomena and allow targeting applications both in solution (bio-conjugation, sensing, imaging) and solid-state (organic electronics, data encryption, lasing, luminescent displays). Excited-State Intramolecular Proton Transfer (ESIPT) fluorescence is particularly suitable to engineer DSE dyes. Indeed, ESIPT fluorescence, which relies on a phototautomerism between normal and tautomeric species, is characterized by a strong emission in the solid-state along with a large Stokes’ shift, an enhanced photostability and a strong sensitivity to the close environment, a feature prone to be used in bio-sensing. A drawback that needs to be overcome is their weak emission intensity in solution, owing to detrimental molecular motions in the excited-state. Several strategies have been proposed in that regard. In the past few years, a growing number of examples of DSE-ESIPT dyes have indeed emerged in the literature, enriching the database of such attractive dyes. This review aims at a brief but concise overview on the exploitation of ESIPT luminescence for the optimization of DSE dyes properties. In that perspective, a synergistic approach between organic synthesis, fluorescence spectroscopy and ab initio calculations has proven to be an efficient tool for the construction and optimization of DSE-ESIPT fluorophores.https://www.mdpi.com/1420-3049/27/8/2443fluorophoresESIPT fluorescencedual-state emissionab initio calculations |
| spellingShingle | Timothée Stoerkler Thibault Pariat Adèle D. Laurent Denis Jacquemin Gilles Ulrich Julien Massue Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept, Examples and Applications Molecules fluorophores ESIPT fluorescence dual-state emission ab initio calculations |
| title | Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept, Examples and Applications |
| title_full | Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept, Examples and Applications |
| title_fullStr | Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept, Examples and Applications |
| title_full_unstemmed | Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept, Examples and Applications |
| title_short | Excited-State Intramolecular Proton Transfer Dyes with Dual-State Emission Properties: Concept, Examples and Applications |
| title_sort | excited state intramolecular proton transfer dyes with dual state emission properties concept examples and applications |
| topic | fluorophores ESIPT fluorescence dual-state emission ab initio calculations |
| url | https://www.mdpi.com/1420-3049/27/8/2443 |
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