Polariton-assisted donor-acceptor role reversal in resonant energy transfer between organic dyes strongly coupled to electromagnetic modes of a tuneable microcavity

TL;DR

This study demonstrates how strong coupling of organic dyes to a tunable microcavity can reverse donor-acceptor roles in energy transfer, enabling remote control of molecular interactions and potential applications in energy harvesting and sensing.

Contribution

The paper introduces a novel polariton-assisted mechanism that reverses donor-acceptor roles in resonant energy transfer within a tunable microcavity, supported by experimental validation.

Findings

Strong coupling induces a large energy shift in donor molecules.

Energy transfer can be reversed, enabling donor-acceptor role reversal.

Cavity detuning controls the population of hybrid states.

Abstract

Resonant interaction between excitonic transitions of molecules and localized electromagnetic field allows the formation of hybrid light-matter polaritonic states. This hybridization of the light and the matter states has been shown to be able to significantly alter the intrinsic properties of molecular ensembles placed inside the optical cavity. Here, we have achieved strong coupling between the excitonic transition in typical oligonucleotide-based molecular beacons labelled with a pair of organic dye molecules, demonstrating an efficient donor to acceptor resonance energy transfer, and the tuneable open-access cavity mode. The photoluminescence of this hybrid system under non-resonant laser excitation and the dependence of the relative population of light-matter hybrid states on cavity detuning have been characterized. Furthermore, by analysing the dependence of the relaxation pathways between energy states in this system, we have demonstrated that predominant strong coupling of the cavity photon to the exciton transition in the donor dye molecule can lead to such a large an energy shift that the energy transfer from the acceptor exciton reservoir to the mainly donor lower polaritonic state can be achieved, thus yielding the chromophores donor-acceptor role reversal or carnival effect. Our experimental data confirm the theoretically predicted possibility for confined electromagnetic fields to control and mediate polariton-assisted remote energy transfer thus paving the way to new approaches to remote-controlled chemistry, energy harvesting, energy transfer and sensing.