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      Direct Transition from Triplet Excitons to Hybrid Light–Matter States via Triplet–Triplet Annihilation

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          Abstract

          Strong light–matter coupling generates hybrid states that inherit properties of both light and matter, effectively allowing the modification of the molecular potential energy landscape. This phenomenon opens up a plethora of options for manipulating the properties of molecules, with a broad range of applications in photochemistry and photophysics. In this article, we use strong light–matter coupling to transform an endothermic triplet–triplet annihilation process into an exothermic one. The resulting gradual on–off photon upconversion experiment demonstrates a direct conversion between molecular states and hybrid light–matter states. Our study provides a direct evidence that energy can relax from nonresonant low energy molecular states directly into hybrid light–matter states and lays the groundwork for tunable photon upconversion systems that modify molecular properties in situ by optical cavities rather than with chemical modifications.

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          Most cited references67

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          Theory of the Contribution of Excitons to the Complex Dielectric Constant of Crystals

          J Hopfield (1958)
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            Single-molecule strong coupling at room temperature in plasmonic nanocavities

            Emitters placed in an optical cavity experience an environment that changes their coupling to light. In the weak-coupling regime light extraction is enhanced, but more profound effects emerge in the single-molecule strong-coupling regime where mixed light-matter states form1,2. Individual two-level emitters in such cavities become non-linear for single photons, forming key building blocks for quantum information systems as well as ultra-low power switches and lasers3–6. Such cavity quantum electrodynamics has until now been the preserve of low temperatures and complex fabrication, severely compromising their use5,7,8. Here, by scaling the cavity volume below 40 nm3 and using host-guest chemistry to align 1-10 protectively-isolated methylene-blue molecules, we reach the strong-coupling regime at room temperature and in ambient conditions. Dispersion curves from >50 plasmonic nanocavities display characteristic anticrossings, with Rabi frequencies of 300 meV for 10 molecules decreasing to 90 meV for single molecules, matching quantitative models. Statistical analysis of vibrational spectroscopy time-series and dark-field scattering spectra provide evidence of single-molecule strong coupling. This dressing of molecules with light can modify photochemistry, opening up the exploration of complex natural processes such as photosynthesis9 and pathways towards manipulation of chemical bonds10.
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              Singlet fission.

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                Author and article information

                Journal
                J Am Chem Soc
                J Am Chem Soc
                ja
                jacsat
                Journal of the American Chemical Society
                American Chemical Society
                0002-7863
                1520-5126
                11 May 2021
                19 May 2021
                : 143
                : 19
                : 7501-7508
                Affiliations
                []Department of Chemistry and Molecular Biology, University of Gothenburg , Kemigården 4, 412 96 Gothenburg, Sweden
                []Department of Physics, Stockholm University , Albanova University Centre, 106 91 Stockholm, Sweden
                Author notes
                Author information
                http://orcid.org/0000-0001-8533-201X
                Article
                10.1021/jacs.1c02306
                8154526
                33973463
                d14adbed-6aa6-40f8-b01c-ecb4d5820337
                © 2021 The Authors. Published by American Chemical Society

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 01 March 2021
                Funding
                Funded by: H2020 European Research Council, doi 10.13039/100010663;
                Award ID: 852286
                Funded by: Knut och Alice Wallenbergs Stiftelse, doi 10.13039/501100004063;
                Award ID: KAW 2017.0192
                Funded by: H2020 European Research Council, doi 10.13039/100010663;
                Award ID: ERC-2017-StG-757733
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                ja1c02306
                ja1c02306

                Chemistry
                Chemistry

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