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<dc:title xml:lang="en">Triarylamine based supramolecular polymers : increasing complexity</dc:title>
<dcterms:alternative xml:lang="fr">L’augmentation de la complexité des polymères supramoléculaires à base de triarylamines</dcterms:alternative>
<dc:subject xml:lang="fr">Chimie supramoléculaire</dc:subject>
<dc:subject xml:lang="fr">Auto-assemblage</dc:subject>
<dc:subject xml:lang="fr">Polymères supramoléculaires</dc:subject>
<dc:subject xml:lang="fr">Chiralité supramoléculaire</dc:subject>
<dc:subject xml:lang="fr">Triarylamine</dc:subject>
<dc:subject xml:lang="fr">Émission induite par agrégation</dc:subject>
<dc:subject xml:lang="fr">Luminescence à polarisation circulaire</dc:subject>
<dc:subject xml:lang="fr">Macrocycle</dc:subject>
<dc:subject xml:lang="fr">Délocalisation</dc:subject>
<dc:subject xml:lang="en">Supramolecular chemistry</dc:subject>
<dc:subject xml:lang="en">Self-assembly</dc:subject>
<dc:subject xml:lang="en">Supramolecular polymers</dc:subject>
<dc:subject xml:lang="en">Supramolecular chirality</dc:subject>
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<dc:subject xml:lang="en">Triarylamine</dc:subject>
<dc:subject xml:lang="en">Aggregation-induced emission</dc:subject>
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<dcterms:abstract xml:lang="fr">Dans cette thèse, nous avons étudié de nouveaux polymères supramoléculaires à base de triarylamine. Dans un premier projet, en profitant du phénomène d'émission induite par agrégation, nous avons réussi à obtenir des polymères supramoléculaires fluorescents ayant des propriétés conductrices de trous. De plus, les composés chiraux, ont conduit à des polymères présentant une hélicité préférentielle et l'émission de luminescence à polarisation circulaire. En ajustant opportunément la structure chimique du monomère, nous avons obtenu un contrôle élevé sur le processus de polymérisation supramoléculaire, ce qui nous a permis d'ajuster les morphologies des assemblages, la chiralité supramoléculaire et les caractéristiques des matériaux finis. Nous avons démontré que l'augmentation du degré d'organisation du système est un moyen approprié pour optimiser les performances de ces matériaux. Dans un deuxième projet, nous avons réussi à mettre au point un moyen approprié de synthétiser un macrocycle à base de triarylamine par une synthèse convergente en plusieurs étapes. La molécule présentait des propriétés électromagnétiques intrigantes, avec l'oxydation en un radical polycationique. Nous avons également réussi à optimiser les conditions de formation des polymères supramoléculaires par l'empilement d'unités macrocycliques de manière unidirectionnelle.</dcterms:abstract>
<dcterms:abstract xml:lang="en">In this thesis we have investigated new triarylamine based supramolecular polymers. In a fist project, by taking advantage from the aggregation-induced emission phenomenon, we succeeded in obtaining fluorescent supramolecular polymers with hole-conductive properties. Moreover, its chiral versions led to polymers showing a preferential helicity and showed circularly polarized luminescence. By adjusting the chemical structure of the monomer, we gained control on the supramolecular polymerization process, which allowed us to tune the morphologies of the assemblies, its supramolecular chirality, and the photo-physical characteristics of the final materials. We demonstrated that increasing the degree of organization of the system is a suitable path to optimize the performance of these materials. In a second project, we succeeded in developing a suitable synthetic methodology to prepare a triarylamine-based macrocycle through a convergent multistep synthesis. The macrocyclic compound, a hexaaza[16]para-cyclophane bearing six amide groups, exhibited intriguing electronic properties during its oxidation to polycationic radicals. We further succeeded in optimizing the conditions for the formation of supramolecular polymers driven by six simultaneous hydrogen bonds and the stacking of macrocyclic units in unidirectional fashion.</dcterms:abstract>
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