Journal
CHEMICAL SCIENCE
Volume 12, Issue 26, Pages 9196-9200Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1sc02225c
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Funding
- Agence Nationale de la Recherche [ANR-16-CE29-0011]
- China Scholarship Council
- European Union's Horizon 2020 Research and Innovation Programme under the Marie Skodowska-Curie grant [796612, 660731]
- CNRS
- Royal Society
- Agence Nationale de la Recherche (ANR) [ANR-16-CE29-0011] Funding Source: Agence Nationale de la Recherche (ANR)
- Marie Curie Actions (MSCA) [660731, 796612] Funding Source: Marie Curie Actions (MSCA)
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This paper demonstrates the first example of bidirectional reversible electronic energy transfer (REET) within a rotaxane, showing that cation binding can modulate the axle chromophore energy levels and provide a luminescence read-out. Modulation of REET processes represents an unexplored mechanism in luminescent molecular sensor development.
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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