Damming an electronic energy reservoir : ion-regulated electronic energy shuttling in a rotaxane
Yu, S., Kupryakov, A., Lewis, J. E. M., Martí-Centelles, V., Goldup, S. M., Pozzo, J.-L., Jonusauskas, G., & McClenaghan, N. D. (2021). Damming an electronic energy reservoir : ion-regulated electronic energy shuttling in a rotaxane. Chemical Science, 12(26), 9196-9200. https://doi.org/10.1039/D1SC02225C
Published inChemical Science
DisciplineOrgaaninen kemiaOrganic Chemistry
© 2021 The Author(s). Published by the Royal Society of Chemistry
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.
PublisherRoyal Society of Chemistry (RSC)
ISSN Search the Publication Forum2041-6520
Publication in research information system
MetadataShow full item record
Additional information about fundingWe 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 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.
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