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<dc:title xml:lang="fr">Tectonique moléculaire : vers la formation de réseaux chiraux par coordination ou liaisons covalentes</dc:title>
<dcterms:alternative xml:lang="en">Molecular tectonic : toward the formation of chiral network using coordination or covalent bonds</dcterms:alternative>
<dc:subject xml:lang="fr">Réseau de coordination</dc:subject>
<dc:subject xml:lang="fr">Réseau covalent cristallin</dc:subject>
<dc:subject xml:lang="fr">Auto-assemblage</dc:subject>
<dc:subject xml:lang="fr">Iridium</dc:subject>
<dc:subject xml:lang="fr">MOF</dc:subject>
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<dc:subject xml:lang="fr">Tectonique moléculaire</dc:subject>
<dc:subject xml:lang="fr">Réseau homochiral</dc:subject>
<dc:subject xml:lang="fr">Réseau hétérométallique</dc:subject>
<dc:subject xml:lang="en">Coordination network</dc:subject>
<dc:subject xml:lang="en">Covalent network</dc:subject>
<dc:subject xml:lang="en">Self-assembly</dc:subject>
<dc:subject xml:lang="en">Iridium</dc:subject>
<dc:subject xml:lang="en">MOF</dc:subject>
<dc:subject xml:lang="en">COF</dc:subject>
<dc:subject xml:lang="en">Molecular tectonics</dc:subject>
<dc:subject xml:lang="en">Homochiral network</dc:subject>
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<tef:elementdEntree autoriteExterne="027837769" autoriteSource="Sudoc">Réseaux cristallins</tef:elementdEntree>
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<tef:elementdEntree autoriteExterne="030016339" autoriteSource="Sudoc">Liaisons de coordination</tef:elementdEntree>
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<tef:elementdEntree autoriteExterne="030016266" autoriteSource="Sudoc">Liaisons covalentes</tef:elementdEntree>
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<dcterms:abstract xml:lang="fr">L’objectif de ce travail fut la conception d’édifices périodiques cristallins chiraux formés par auto-assemblage de briques de construction préprogrammées appelées (métalla)tectons via des liaisons de coordination (MOF) ou des liaisons covalentes (COF). Dans le premier chapitre, la synthèse de complexes cationiques d’iridium(III) cyclométallés racémiques et énantiopures substitués par des groupements pyridines ou acides benzoïques a été mise au point. Ces métallatectons ont permis l’obtention de nouveaux réseaux hétérométalliques par auto-assemblage avec divers cations métalliques. Un réseau homochiral bi-dimensionnel de type grille a pu être obtenu. Le second chapitre s’intéresse à la formation de COFs cristallins. De nouveaux tectons portant deux unités catécholates reliées par une chaîne polyéthylèneglycol ont été synthétisés afin de générer des réseaux homochiraux hélicoïdaux. Ces tectons, en présence d’acide borique et d’une base alcaline, devant permettre l’enroulement de la chaîne polyéthylèneglycol, ont cependant uniquement mené à la formation d’entités oligomériques.</dcterms:abstract>
<dcterms:abstract xml:lang="en">The aim of this PhD work was to design new homochiral molecular networks using either coordination (MOF) or covalent bonds (COF) applying the concepts of molecular tectonics that deal with the formation of crystalline periodic architectures formed upon self-assembly of preprogrammed building blocks known as (metalla)tectons. In the first part, the synthesis of cationic cyclometalated iridium(III) complexes substituted with pyridine or benzoic acid derivatives, as racemic mixture or enantiomerically pure, has been carried out. Upon self-assembly of those metallatectons with distinct metallic cations, heterometallic coordination networks were obtained. Notably, a 2-D grid-type homochiral coordination network was successfully synthetized. The second part focused on the generation of homochiral helical crystalline covalent networks. Novel organic tectons using two catecholate units connected by a polyethyleneglycol chain have been synthesized. Reaction of these tectons with boric acid and an alkaline base, enabling the chain winding around the alkaline cation, has only led to the formation of oligomeric architectures.</dcterms:abstract>
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