Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane
Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane
We demonstrate the first example of bidirectional reversible electronic energy transfer (REET) between the mechanically bonded components of a rotaxane. Our prototypical system was designed such that photoexcitation of a chromophore in the axle results in temporary storage of electronic energy in a quasi-isoenergetic “reservoir” chromophore in the macrocycle. Over time, the emissive state of the axle is repopulated from this reservoir, resulting in long-lived, delayed luminescence. Importantly, we show that cation binding in the cavity formed by the mechanical bond perturbs the axle chromophore energy levels, modulating the REET process, and ultimately providing a luminescence read-out of cation binding. Modulation of REET processes represents an unexplored mechanism in luminescent molecular sensor development.
9196-9200
Yu, Shilin
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Kupryakov, Arkady
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Lewis, James EM
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Martí-Centelles, Vicente
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Goldup, Stephen
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Pozzo, Jean-Luc
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Jonusauskas, Gediminas
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McClenaghan, Nathan D.
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Yu, Shilin
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Kupryakov, Arkady
63bc22a4-67b3-4210-bf46-bbb9a0a72f82
Lewis, James EM
42b46a03-a7ca-4d3a-96e5-a5c962fc9573
Martí-Centelles, Vicente
78157d58-a98a-4c4a-a971-e14449a8e119
Goldup, Stephen
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Pozzo, Jean-Luc
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Jonusauskas, Gediminas
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McClenaghan, Nathan D.
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Yu, Shilin, Kupryakov, Arkady, Lewis, James EM, Martí-Centelles, Vicente, Goldup, Stephen, Pozzo, Jean-Luc, Jonusauskas, Gediminas and McClenaghan, Nathan D.
(2021)
Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane.
Chemical Science, 12 (26), .
(doi:10.1039/D1SC02225C).
Abstract
We demonstrate the first example of bidirectional reversible electronic energy transfer (REET) between the mechanically bonded components of a rotaxane. Our prototypical system was designed such that photoexcitation of a chromophore in the axle results in temporary storage of electronic energy in a quasi-isoenergetic “reservoir” chromophore in the macrocycle. Over time, the emissive state of the axle is repopulated from this reservoir, resulting in long-lived, delayed luminescence. Importantly, we show that cation binding in the cavity formed by the mechanical bond perturbs the axle chromophore energy levels, modulating the REET process, and ultimately providing a luminescence read-out of cation binding. Modulation of REET processes represents an unexplored mechanism in luminescent molecular sensor development.
Text
d1sc02225c
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Accepted/In Press date: 4 June 2021
e-pub ahead of print date: 4 June 2021
Additional Information:
Funding Information:
We are grateful for nancial support from the Agence Nationale de la Recherche [grant number ANR-16-CE29-0011], China Scholarship Council (S. Y.), European Union's Horizon 2020 Research and Innovation Programme under the Marie Skłodowska-Curie grant agreements: no. 796612 (V. M.-C.) & no. 660731 (J. E. M. L.) and CNRS. SMG thanks the Royal Society for a Wolfson Research Fellowship.
Funding Information:
We are grateful for financial support from the Agence Nationale de la Recherche [grant number ANR-16-CE29-0011], China Scholarship Council (S. Y.), European Union's Horizon 2020 Research and Innovation Programme under the Marie Sk?odowska-Curie grant agreements: no. 796612 (V. M.-C.) & no. 660731 (J. E. M. L.) and CNRS. SMG thanks the Royal Society for a Wolfson Research Fellowship.
Publisher Copyright:
© The Royal Society of Chemistry 2021.
Identifiers
Local EPrints ID: 449971
URI: http://eprints.soton.ac.uk/id/eprint/449971
ISSN: 1478-6524
PURE UUID: 925f48b9-6546-41aa-8592-c723ce113f87
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Date deposited: 01 Jul 2021 16:30
Last modified: 05 Jun 2024 17:37
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Contributors
Author:
Shilin Yu
Author:
Arkady Kupryakov
Author:
James EM Lewis
Author:
Vicente Martí-Centelles
Author:
Jean-Luc Pozzo
Author:
Gediminas Jonusauskas
Author:
Nathan D. McClenaghan
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