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

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.

Automated summary

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.