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

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)
37 Downloads (Pure)


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 languageEnglish
Pages (from-to)9196-9200
Number of pages5
JournalChemical Science
Issue number26
Early online date4 Jun 2021
Publication statusPublished - 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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