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<dc:title xml:lang="en">Supramolecular catalysis and vibrational strong coupling : how to influence chemical reactivity ?</dc:title>
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<dc:subject xml:lang="fr">Catalyse supramoléculaire</dc:subject>
<dc:subject xml:lang="fr">Isochromanes</dc:subject>
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<dc:subject xml:lang="fr">Couplage fort vibrationnel</dc:subject>
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<dc:subject xml:lang="en">Supramolecular catalysis</dc:subject>
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<dc:subject xml:lang="en">Vibrational strong coupling</dc:subject>
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<dcterms:abstract xml:lang="fr">Comment peut-on influencer la réactivité chimique ? Dans ce travail de thèse, j’ai tâché de répondre à cette question en explorant la frontière entre la chimie et la physique. Dans un premier temps, en tirant avantage du solvant 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) qui permet souvent une réactivité exotique, qui peut être attribuée à ses exceptionnelles propriétés physiques. Ces dernières font de HFIP une véritable matrice supramoléculaire, qui nous a permis le développement d’une nouvelle méthode pour la synthèse d’isochromanes fonctionnalisés. Ce faisant, une généralité et une simplicité opératoire inédites pour la synthèse de ce motif important furent atteintes. Dans un second temps, j’ai exploré la capacité de l’hybridation lumière-matière, accessible grâce au couplage fort vibrationnel (CFV) de modifier la cinétique de certaines réactions chimiques. Ainsi, en plaçant entre deux miroirs différents réactifs, j’ai étudié l’impact du CFV sur la nucléophilicité ainsi que sur la réactivité Diels-Alder.</dcterms:abstract>
<dcterms:abstract xml:lang="en">How can we influence chemical reactivity? Throughout this thesis, I attempted to answer this question by exploring the frontier between chemistry and physics.First, I took advantage of solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) which often unlocks exotic reactivity that can be explained by its extraordinary physical properties. These properties make of HFIP a veritable supramolecular matrix, which allowed the development of a new method for the synthesis of densely functionalized isochromans. This method displayed unprecedented generality, simplicity, and practicality on the way to this pharmacologically important motif.Second, I investigated how light-matter hybridization, accessed through Vibrational Strong Coupling (VSC) could alter the kinetics of some chemical reactions. In practice, by placing different reactants between two mirrors, I studied the impact of VSC on nucleophilicity, as well as on Diels-Alder reactivity.</dcterms:abstract>
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