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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.

SUBMITTER: Yu S

PROVIDER: S-EPMC8261707 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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

Yu Shilin S Kupryakov Arkady A Lewis James E M JEM Martí-Centelles Vicente V Goldup Stephen M SM Pozzo Jean-Luc JL Jonusauskas Gediminas G McClenaghan Nathan D ND

Chemical science 20210604 26

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, ...[more]

PMID: 34276950

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