Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane

Shilin Yu; Arkady Kupryakov; James E.M. Lewis; Vicente Martí-Centelles; Stephen M. Goldup; Jean Luc Pozzo; Gediminas Jonusauskas; Nathan D. McClenaghan

doi:10.1039/d1sc02225c

Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane

Shilin Yu, Arkady Kupryakov, James E.M. Lewis, Vicente Martí-Centelles, Stephen M. Goldup^*, Jean Luc Pozzo, Gediminas Jonusauskas, Nathan D. McClenaghan^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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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.

Original language	English
Pages (from-to)	9196-9200
Number of pages	5
Journal	Chemical Science
Volume	12
Issue number	26
Early online date	4 Jun 2021
DOIs	https://doi.org/10.1039/d1sc02225c
Publication status	Published - 14 Jul 2021

Bibliographical note

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.

Publisher Copyright:
© The Royal Society of Chemistry 2021.

ASJC Scopus subject areas

General Chemistry

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10.1039/d1sc02225cLicence: Creative Commons: Attribution (CC BY)

YuS2021DammingFinal published version, 701 KBLicence: Creative Commons: Attribution (CC BY)

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@article{508024779f63401d9b57e206ac12fa89,

title = "Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane",

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.",

author = "Shilin Yu and Arkady Kupryakov and Lewis, {James E.M.} and Vicente Mart{\'i}-Centelles and Goldup, {Stephen M.} and Pozzo, {Jean Luc} and Gediminas Jonusauskas and McClenaghan, {Nathan D.}",

note = "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 Sk{\l}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: {\textcopyright} The Royal Society of Chemistry 2021.",

year = "2021",

month = jul,

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doi = "10.1039/d1sc02225c",

language = "English",

volume = "12",

pages = "9196--9200",

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T1 - Damming an electronic energy reservoir

T2 - ion-regulated electronic energy shuttling in a [2]rotaxane

AU - Yu, Shilin

AU - Kupryakov, Arkady

AU - Lewis, James E.M.

AU - Martí-Centelles, Vicente

AU - Goldup, Stephen M.

AU - Pozzo, Jean Luc

AU - Jonusauskas, Gediminas

AU - McClenaghan, Nathan D.

N1 - 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. Publisher Copyright: © The Royal Society of Chemistry 2021.

PY - 2021/7/14

Y1 - 2021/7/14

N2 - 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.

AB - 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.

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JO - Chemical Science

JF - Chemical Science

IS - 26

ER -

Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane

Abstract

Bibliographical note

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