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<dc:title xml:lang="fr">Multi-porphyrines et interactions avec des polyoxométallates</dc:title>
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<dc:subject xml:lang="fr">Porphyrine</dc:subject>
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<dc:subject xml:lang="fr">Chimie supramoléculaire</dc:subject>
<dc:subject xml:lang="fr">Electrochimie</dc:subject>
<dc:subject xml:lang="fr">Photochimie</dc:subject>
<dc:subject xml:lang="fr">Complexe organique-inorganique</dc:subject>
<dc:subject xml:lang="en">Porphyrin</dc:subject>
<dc:subject xml:lang="en">Polyoxometalate</dc:subject>
<dc:subject xml:lang="en">Supramolecular chemistry</dc:subject>
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<dc:subject xml:lang="en">Fluorescence</dc:subject>
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<dcterms:abstract xml:lang="fr">Ce travail décrit l’étude de l’encapsulation de polyoxométallate (POM) au sein de dimères de porphyrines cationiques. Différentes voies de synthèse ont été étudiées pour l’accessibilité de ces dimères cationiques. Dans un premier temps, la formation des molécules a été entreprise par couplage pyridine /porphyrine induit par voie électrochimique. Cependant, les résultats ont montré qu’il est difficile d’utiliser des systèmes multi-porphyriniques en raison de la réactivité des cations radicalaires des porphyrines. Une approche chimique alternative a permis de générer des dimères cationiques par formation de liaisons N-C(benzylique) et cette stratégie peut être étendue à une grande variété d’espaceurs, de type xylyle ou imidazole. L’inclusion de POM dans des dimères de porphyrines en solution a été étudiée par fluorescence et a permis de mettre en évidence la formation d’assemblages polyoxométallate-porphyrines. Le suivi de cette formation en UV-visible et fluorescence suggère que les interactions entre le POM et la porphyrine sont majoritairement des interactions faibles (van der Waals et électrostatiques).</dcterms:abstract>
<dcterms:abstract xml:lang="en">This work describes the study of polyoxometalate (POM) encapsulation in cationic porphyrin dimers. Several synthetic pathways have been studied to prepare these cationic dimers. Initially, the synthesis of molecules was undertaken by pyridine/porphyrin coupling induced by electrochemistry. However, the synthesis of multi-porphyrin systems was difficult due to the reactivity of the porphyrin radical cations. An alternative chemical approach has generated cationic dimers by the formation of N-C(benzyl) bonds and this strategy can be extended to a wide variety of spacers, from xylyl derivatives to imidazole. The inclusion of a POM in porphyrin dimers in solution was studied by fluorescence, which highlighted the formation of polyoxometalate-porphyrin assemblies. The UV-visible titration suggests that the interactions between POM and porphyrin are mainly weak interactions (van der Waals and electrostatic).</dcterms:abstract>
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