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<dc:title xml:lang="en">Chiral organometallic concave compounds : luminescence and supramolecular properties</dc:title>
<dcterms:alternative xml:lang="fr">Composés organométalliques concaves chiraux : propriétés supramoléculaires et de luminescence</dcterms:alternative>
<dc:subject xml:lang="fr">Cyclotribenzylène</dc:subject>
<dc:subject xml:lang="fr">Complexe alcyne-metal noble</dc:subject>
<dc:subject xml:lang="fr">Émission induite par l'agrégation</dc:subject>
<dc:subject xml:lang="fr">Chiralité</dc:subject>
<dc:subject xml:lang="fr">Pré-cryptophane</dc:subject>
<dc:subject xml:lang="en">Cyclotribenzylene</dc:subject>
<dc:subject xml:lang="en">Alkynyl noble metal complex</dc:subject>
<dc:subject xml:lang="en">Aggregation-induced emission</dc:subject>
<dc:subject xml:lang="en">Chirality</dc:subject>
<dc:subject xml:lang="en">Precryptophane</dc:subject>
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<tef:elementdEntree autoriteExterne="028631463" autoriteSource="Sudoc">Chiralité</tef:elementdEntree>
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<tef:elementdEntree autoriteExterne="190215453" autoriteSource="Sudoc">Cryptophanes</tef:elementdEntree>
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<dcterms:abstract xml:lang="fr">Nous avons exploré deux voies de synthèse de métallo-cryptophanes dans le but de créer des récepteurs douésde propriétés photophysiques originales. Dans une première partie nous avons synthétisé des complexes deAu(I) avec des cyclotribenzylènes (CTB) à fonctions alcynes afin dévaluer la capacité de ces composés à formerdes cryptophanes par interactions aurophiles. Les complexes sont luminescents dans CHCl3 et complexent lesammoniums quaternaires comme Et4N+. Les complexes dans MeOH/ CHCl3 s'auto-assemblentstéréosélectivement pour former des agrégats sphériques à des taux de MeOH élevés, le début de l'agrégationdépendant de la nature des ligands. Dans la deuxième partie, nous présentons la synthèse de pré-cryptophanesde platine à partir d'un CTB substitué par une fonction alcyne vraie et deux fonctions carbonitrile. Ces composésont été isolés, de manière inattendue, sous forme de complexes de Cu(I). Les conformations des précryptophanessans Cu ont été étudiées dans différents solvants et dépendent des configurations relatives desCTB. Ces études ont ouvert la voie à de nouvelles approches synthétiques de crytophanes organométalliques.</dcterms:abstract>
<dcterms:abstract xml:lang="en">We explored two ways for new approaches of metallo-cryptophane design and synthesis to create receptorsendowed with original photophysical properties. In Part I, we synthesized alkynyl cyclotribenzylene (CTB)gold(I) complexes for evaluating their ability to form cryptophanes using aurophilic interactions. Theorganometallic CTBs were found to be luminescent in CHCl3 and able to host quaternary ammoniums like Et4N+.Studies of optically-active and racemic gold CTB complexes in MeOH/CHCl3 showed that they self-assembledstereoselectively into spherical nanoparticles at high MeOH content, the onset of nanoparticle formationdepending on the nature of the metal ligands. In Part , luminescent organoplatinum precryptophanes weresynthe-sized from a CTB containing an alkynyl and two carbonitrile substituents. They were unexpectedlyisolated as Cu(I) complexes. The conformations of the Cu-free precryptophanes were studied in differentsolvents and were shown to depend also on the relative configurations of the two CTBs. These experimentspaved the way for finding new strategies for the synthesis of organometallic cryptophanes.</dcterms:abstract>
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