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<dc:title xml:lang="en">Synthesis and electrochemical investigation of modified viologens capable of radical-radical interactions</dc:title>
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<dc:subject xml:lang="fr">Interactions radical-radical</dc:subject>
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<dc:subject xml:lang="fr">Chimie hôte–invité</dc:subject>
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<dc:subject xml:lang="en">Radical-radical interactions</dc:subject>
<dc:subject xml:lang="en">Viologens</dc:subject>
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<dcterms:abstract xml:lang="fr">Cette thèse de doctorat explore les interactions radical–radical dans des systèmes à base de viologènes non conventionnels, afin d’éclairer leur comportement électrochimique et leurs mécanismes rédox au sein d’architectures supramoléculaires hôte–invité. Une synthèse améliorée du cyclobis(paraquat-p-phénylène) fonctionnalisé par un alcyne est présentée. Cette plateforme a permis la création de dérivés multitopiques, répondant à une lacune où seule la composante axiale des (pseudo)rotaxanes était modifiée. Ces systèmes ont révélé une homodimérisation spontanée inédite, affectant la complexation hôte–invité. Enfin, des viologènes porteurs d’un accepteur de type Michael ont été développés, montrant des interactions dépendantes du solvant avec les cyclophanes. L’addition de Michael permet de rompre ces interactions, offrant un nouveau moyen de contrôler l’assemblage supramoléculaire.</dcterms:abstract>
<dcterms:abstract xml:lang="en">This PhD thesis explores radical–radical interactions in unconventional viologen-based systems, to deepen the understanding of their electrochemical behaviour and redox mechanisms within supramolecular host-guest architectures. An improved synthesis of alkyne-functionalized cyclobis(paraquat-p-phenylene) is presented. This versatile platform enabled the construction of multitopic paraquat derivatives, addressing a gap in the literature where design efforts focused mainly on the axle component of (pseudo)rotaxanes. These multitopic systems revealed unprecedented spontaneous homodimerization, significantly affecting host-guest complexation. Finally, viologens bearing Michael acceptor groups were developed, showing solvent-dependent interactions with cyclophanes. Michael addition was used to chemically disrupt radical-radical interactions, offering new control over supramolecular assembly.</dcterms:abstract>
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