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Article Dans Une Revue Angewandte Chemie Année : 2024

Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy

Résumé

Polaritonic chemistry is emerging as a powerful approach to modifying the properties and reactivity of molecules and materials. However, probing how the electronics and dynamics of molecular systems change under strong coupling has been challenging due to the narrow range of spectroscopic techniques that can be applied in situ. Here we develop microfluidic optical cavities for vibrational strong coupling (VSC) that are compatible with nuclear magnetic resonance (NMR) spectroscopy using standard liquid NMR tubes. VSC is shown to influence the equilibrium between two conformations of a molecular balance sensitive to dispersion forces, revealing a clear change in the equilibrium constant under VSC. In all compounds studied, VSC does not induce detectable changes in chemical shifts, J-couplings, or spin-lattice relaxation times. This unexpected finding indicates that VSC does not substantially affect molecular electron density distributions, and in turn has profound implications for the possible mechanisms at play in polaritonic chemistry under VSC and suggests that the emergence of collective behavior is critical.
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Origine : Publication financée par une institution
Licence : CC BY NC ND - Paternité - Pas d'utilisation commerciale - Pas de modification

Dates et versions

hal-04348012 , version 1 (15-12-2023)
hal-04348012 , version 2 (03-05-2024)

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Bianca Patrahau, Maciej Piejko, Robert Josef Mayer, Cyril Antheaume, Thitiporn Sangchai, et al.. Direct Observation of Polaritonic Chemistry by Nuclear Magnetic Resonance Spectroscopy. Angewandte Chemie, 2024, pp.e202401368. ⟨10.1002/anie.202401368⟩. ⟨hal-04348012v2⟩
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