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Radicaux π-conjugués pour la construction et le contrôle redox d'assemblages moléculaires organisés

Abstract : The aim of the thesis is to develop new concepts in the design of redox-switchable molecular and supramolecular architectures. The strategies which have been implemented rely on the π-dimerization of viologen radical cations as a driving force for the generation of electron-triggered intramolecular movements. Upon studying a series of viologen-appended calixarenes, we have established that bipyridinium radicals can be reversibly -dimerized under the joined effects of chemical (proton transfer) and electrochemical (electron transfer) stimulus. Our investigations also led to the discovery that a bis-pyridinyl appended calixarene intermediate is involved in a fully reversible redox-triggered sigma-dimerization process. We have also established that the ability of a phenol-containing calixarene to dimerize in its two electron reduced state depends on a subtle balance of weak interactions associated with hydrogen bond formation on the lower rim and orbital overlap between -radicals on the upper rim.We also demonstrate that inorganic hinges based on palladium complexes can be used as pivots in viologen-containing π-dimerizable architectures. The redox-controlled self-assemby of dynamic coordination polymers is also addressed through two examples of molecular tweezers, whose arms are functionalized by self-complementary complexing units or by bidentate ligands. In a last example, a palladium metal center is used both as a carrier of polymerization and as a hinge enabling the intramolecular π-dimerization of ditopic viologen-based ligands.
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Submitted on : Tuesday, January 2, 2018 - 1:34:18 AM
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  • HAL Id : tel-01674189, version 1


Christophe Kahlfuss. Radicaux π-conjugués pour la construction et le contrôle redox d'assemblages moléculaires organisés. Chimie organique. Ecole normale supérieure de lyon - ENS LYON, 2015. Français. ⟨NNT : 2015ENSL1030⟩. ⟨tel-01674189⟩



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