Polariton-assisted manipulation of energy relaxation pathways: donor–acceptor role reversal in a tuneable microcavity

Dovzhenko, Dmitriy; Lednev, Maksim; Mochalov, Konstantin; Vaskan, Ivan; Rakovich, Yury; Karaulov, Alexander; Nabiev, Igor

doi:10.1039/d1sc02026a

Cited by 22 publications

(10 citation statements)

References 47 publications

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“…Coupling of vibrational excitations to infrared cavities has led to dramatic changes in thermal reaction rates. − The influence of optical polaritons on photochemical processes has received comparatively less attention. Although some works show negligible changes in photophysics due to strong coupling, , other studies of optical cavities have demonstrated polaritonic effects on spin or energy conversion processes such as intersystem crossing, triplet–triplet annihilation, resonant energy transfer, delayed fluorescence, and photobleaching. − …”

Section: Introductionmentioning

confidence: 99%

Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Zeng,

Pérez-Sánchez,

Eckdahl

et al. 2023

J. Am. Chem. Soc.

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Section: Introductionmentioning

confidence: 99%

Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Zeng,

Pérez-Sánchez,

Eckdahl

et al. 2023

J. Am. Chem. Soc.

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“…For such cases, the low energy exciton will be the major contributor to the middle polariton. Thus, the energetics and the direction of energy transfer are reversed . The reversal in energy transfer from the acceptor to the donor in the strong coupling regime has been explained theoretically. , …”

Section: The Fabry–perot Cavitymentioning

confidence: 96%

The Rise and Current Status of Polaritonic Photochemistry and Photophysics

Bhuyan,

Mony,

Kotov

et al. 2023

Chem. Rev.

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The interaction between molecular electronic transitions and electromagnetic fields can be enlarged to the point where distinct hybrid light–matter states, polaritons, emerge. The photonic contribution to these states results in increased complexity as well as an opening to modify the photophysics and photochemistry beyond what normally can be seen in organic molecules. It is today evident that polaritons offer opportunities for molecular photochemistry and photophysics, which has caused an ever-rising interest in the field. Focusing on the experimental landmarks, this review takes its reader from the advent of the field of polaritonic chemistry, over the split into polariton chemistry and photochemistry, to present day status within polaritonic photochemistry and photophysics. To introduce the field, the review starts with a general description of light–matter interactions, how to enhance these, and what characterizes the coupling strength. Then the photochemistry and photophysics of strongly coupled systems using Fabry–Perot and plasmonic cavities are described. This is followed by a description of room-temperature Bose–Einstein condensation/polariton lasing in polaritonic systems. The review ends with a discussion on the benefits, limitations, and future developments of strong exciton–photon coupling using organic molecules.

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“…Some theoretical work predicts large effects of electronic strong coupling on photochemistry, including modifications of potential energy surfaces along which reactions evolve. ,− Despite these advances, and multiple experimental demonstrations of energy-level tuning and rate inversions in molecular systems, ,− there are few experimental demonstrations of polariton-driven chemical transformations in the electronic strong-coupling regime. A pioneering study by Ebbesen and co-workers showed that the rate of the ring-opening photoisomerization of spiropyran (SP) into merocyanine (MC) was slowed by approximately an order of magnitude in cavities that were tuned to be resonant with the product state .…”

Section: Introductionmentioning

confidence: 99%

Controlling Molecular Photoisomerization in Photonic Cavities through Polariton Funneling

Lee,

Melton,

et al. 2024

J. Am. Chem. Soc.

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Strong coupling between photonic modes and molecular electronic excitations, creating hybrid light-matter states called polaritons, is an attractive avenue for controlling chemical reactions. Nevertheless, experimental demonstrations of polaritonmodified chemical reactions remain sparse. Here, we demonstrate modified photoisomerization kinetics of merocyanine and diarylethene by coupling the reactant's optical transition with photonic microcavity modes. We leverage broadband Fourier-plane optical microscopy to noninvasively and rapidly monitor photoisomerization within microcavities, enabling systematic investigation of chemical kinetics for different cavity-exciton detunings and photoexcitation conditions. We demonstrate three distinct effects of cavity coupling: first, a renormalization of the photonic density of states, akin to a Purcell effect, leads to enhanced absorption and isomerization rates at certain wavelengths, notably red-shifting the onset of photoisomerization. This effect is present under both strong and weak light-matter couplings. Second, kinetic competition between polariton localization into reactive molecular states and cavity losses leads to a suppression of the photoisomerization yield. Finally, our key result is that in reaction mixtures with multiple reactant isomers, exhibiting partially overlapping optical transitions and distinct isomerization pathways, the cavity resonance can be tuned to funnel photoexcitations into specific reactant isomers. Thus, upon decoherence, polaritons localize into a chosen isomer, selectively triggering the latter's photoisomerization despite initially being delocalized across all isomers. This result suggests that careful tuning of the cavity resonance is a promising avenue to steer chemical reactions and enhance product selectivity in reaction mixtures.

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Polariton-assisted manipulation of energy relaxation pathways: donor–acceptor role reversal in a tuneable microcavity

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...

Cited by 22 publications

References 47 publications

Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

Control of Photoswitching Kinetics with Strong Light–Matter Coupling in a Cavity

The Rise and Current Status of Polaritonic Photochemistry and Photophysics

Controlling Molecular Photoisomerization in Photonic Cavities through Polariton Funneling

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