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Garci, Amine
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Garci, Amine
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Voici les éléments 1 - 8 sur 8
- PublicationAccès libreInsight into the rules dictating the formation of arene ruthenium metalla-assemblies(2015)
; Le processus d'auto-assemblage est un phénomène naturel capable d'organiser des systèmes biologiques. Son utilisation par les chimistes comme procédé de synthèse a permis la formation de structures esthétiques et de systèmes supramoléculaires hautement complexes, avec des fonctions biologiques avérées. Depuis 1990, la stratégie d'auto-assemblage dirigée par des métaux a largement contribué à la conception et à la synthèse d'architectures discrètes. La formation de ces architectures spécifiques nécessite un contrôle minutieux des différents facteurs dirigeant le processus d'auto-assemblage.
L'objectif de cette thèse est d'offrir un aperçu des règles dictant la formation des assemblages métalliques arène-ruthénium. Ceux-ci sont construits à l’aide de clips métalliques stables et de ligands polypyridiniques. La caractérisation des échanges dynamiques des ligands, au moyen d’une stratégie de marquage isotopique 1H/2D a démontré la stabilité et l'inertie relative de la structure rectangulaire. En outre, l'étude par résonance magnétique nucléaire, des espèces intermédiaires impliquées dans l'assemblage de cycles métalliques, a permis de mettre en exergue la nature dynamique de la liaison Ru-N en solution, avant la fermeture définitive des cycles métalliques. Cela nous a permis de décrire une voie de germination thermodynamique plausible avec une réactivité spécifique de ces assemblages métalliques.
Par ailleurs, l’activité anticancéreuse prometteuse des complexes mononucléaires arène-ruthénium, ainsi que l’accumulation préférentielle de leurs espèces macromoléculaires dans les cellules cancéreuses, confèrent un potentiel antiprolifératif très intéressant aux cages métalliques arène-ruthénium. Ainsi notre stratégie pour optimiser l'activité biologique des prismes métalliques comportait deux approches. Dans un premier temps, la fonctionnalisation des ligands pontés, a permis d’améliorer la sélectivité des composés actifs contre les cellules cancéreuses. Dans un second temps, la modification de la taille des ouvertures, de la cavité des cages métalliques, a permis de contrôler la libération d’un photosensibilisateur hydrophobe dans une lignée cellulaire humaine du cancer du côlon HT-29., The self-assembly process is a natural phenomenon with the ability to organize biological systems. Its development by chemists as a synthetic process allowed the formation of esthetical structures as well as highly complex supramolecular systems with remarkable biological functions. Since 1990, metal directed self-assembly strategy has largely contributed to the design and synthesis of discrete architectures. The formation of these specific architectures needs some control over the different factors ruling the coordination self-assembly process.
The aim of this thesis was to offer an insight into the rules dictating the formation of arene ruthenium metalla-assemblies built from stable dinuclear metalla-clips and polypyridyl linkers. The characterization of the dynamic ligand exchanges using the 1H/2D isotope labeling strategy showed relative stability and inertness of the final structure. In addition, the study of the intermediate species involved during the assembly of metalla-cycles by NMR experiments highlighted the dynamic nature of the Ru-N bond in solution before the final closure of the metalla-cycles. This helped us to describe a plausible thermodynamic germination pathway together with the specific reactivity of such metalla-assemblies.
The promising anticancer-activities of the mononuclear arene ruthenium complexes along with the preferential accumulation of macromolecular species in the cancer cells led to more interest in the anti-proliferative potential of arene ruthenium metalla-cages. Our strategies in order to optimize the biological activity of arene ruthenium metalla-prisms were: Functionalization of the bridging linkers resulted in selectivity improvements of the active compounds towards target cancer cells; and the modification of the portal’s size of metalla-cages to control the release of a hydrophobic photosensitizer on the human colon cancer cell line HT-29. - PublicationMétadonnées seulementElectron-Rich Arene-Ruthenium Metalla-architectures Incorporating Tetrapyridyl-Tetrathiafulvene Donor Moieties(2014)
; ; Salle, MarcA series of arene ruthenium architectures have been prepd. from coordination-driven self-assembly using dinuclear p-cymene ruthenium acceptors and ?-donating tetratopic tetrapyridyl-tetrathiafulvalene donor ligands. The synthetic strategy, based on a geometric interaction approach, leads to four electroactive metalla-assemblies, 1-4 (one mol. cube and three metallaplates), that were characterized by NMR, ESI-MS, X-ray diffraction, and cyclic voltammetry. Rationalization of their formation discrepancy was completed by DFT calcns. supported by structural features of their constituting TTF and Ru-complex components. Metalla-architectures possessing electron-rich cores (3, cis-4, and trans-4) interact strongly with picric acid (PA) to yield cocrystd. products, PA + metalla-assemblies, confirmed by single-crystal X-ray structure analyses. [on SciFinder(R)] - PublicationMétadonnées seulementInsight into the dynamic ligand exchange process involved in bipyridyl linked arene ruthenium metalla-rectangles(2014)
; - PublicationMétadonnées seulementSynthesis, molecular structure, computational study and in vitro anticancer activity of dinuclear thiolato-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) complexes(2013)
; ; Neutral dinuclear dithiolato-bridged pentamethylcyclopentadienyl Rh(III) complexes (C5Me5)2Rh2(?-SR)2Cl2 (R = CH2Ph, 1; R = CH2CH2Ph, 2) and cationic dinuclear trithiolato-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) complexes [(C5Me5)2M2(?-SR)3]+ (M = Rh, R = CH2Ph, 3; M = Rh, R = CH2CH2Ph, 5; M = Rh, R = CH2C6H4-p-tBu, 7: M = Ir, R = CH2Ph, 4; M = Ir, R = CH2CH2Ph, 6; M = Ir, R = CH2C6H4-p-tBu, 8) were synthesized from the chloro-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) dimers (C5Me5)2M2(?-Cl)2Cl2 by reaction with the corresponding thiol deriv. (RSH). Complexes 3-8 were isolated as chloride salts. All complexes were obtained in good yield and were fully characterized by spectroscopic methods. The mol. structures of the neutral complexes (1 and 2) show interesting features: the two Rh atoms are bridged by two thiolato ligands with no metal-metal bonds and the pentamethylcyclopentadienyl and chlorido ligands are oriented syn to each other, an uncommon conformation for such dinuclear complexes. These structural features were rationalized using DFT calcns. Addnl., the antiproliferative activity of the complexes was evaluated against the cancerous A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) human ovarian cell lines and on the noncancerous HEK293 human embryonic kidney cells. All complexes are active and the cationic Ir complexes 4, 6 and 8 are particularly cytotoxic, with IC50 values in the nanomolar range (IC50 < 0.1 ?M). The catalytic activity of the complexes for the oxidn. of glutathione (GSH) to GSSG was evaluated by NMR spectroscopy. [on SciFinder(R)] - PublicationMétadonnées seulementSynthesis, characterisation and in vitro anticancer activity of hexanuclear thiolato-bridged arene ruthenium metalla-prisms(2013)
; ; Hexanuclear hexacationic thiolato-bridged arene ruthenium metalla-prisms of the general formula [[(?6-p-cymene)Ru]6(?-SR)6(?3-tpt)2][OTf]6 (R = CH2Ph, CH2C6H4-p-tBu, CH2CH2Ph; tpt = 2,4,6-tri-4-pyridyl-1,3,5-triazine), obtained from the self-assembly of dinuclear precursors [(p-cymene)2Ru2(?-SR)2Cl2] with tpt and AgCF3SO3, have been isolated and fully characterized as triflate salts. The metalla-prisms are highly cytotoxic against human ovarian cancer cells, esp. towards the cisplatin-resistant cell line A2780cisR (IC50 - PublicationAccès libreDichlorido(furfurylamine-κN)(η6-hexamethylbenzene)ruthenium(II)(2011)
; ; The single-crystal X-ray structure analysis of [RuCl2(C12H18)(C5H7NO)] reveals a distorted piano-stool geometry around the RuII atom, with a hexamethylbenzene ligand, two chloride ligands and a furfurylamine ligand, the latter coordinating through the amine group. In the crystal, a dimeric structure is observed as a result of N-H...Cl interactions between two symmetry-related molecules. - PublicationMétadonnées seulementDichlorido(furfuryl-amine-?N)(?-hexa-methyl-benzene)-ruthenium(II)(2011)
; ; The single-crystal X-ray structure analysis of [RuCl(2)(C(12)H(18))(C(5)H(7)NO)] reveals a distorted piano-stool geometry around the Ru(II) atom, with a hexa-methyl-benzene ligand, two chloride ligands and a furfuryl-amine ligand, the latter coordinating through the amine group. In the crystal, a dimeric structure is observed as a result of N-H(midline ellipsis)Cl inter-actions between two symmetry-related mol-ecules.[on SciFinder (R)] - PublicationMétadonnées seulementDichlorido(furfurylmine-?N)(?6-hexamethylbenzene)ruthenium(II)(2011)
; ; The single-crystal x-ray structure anal. of [RuCl2(C12H18)(C5H7NO)] reveals a distorted piano-stool geometry around the RuII atom, with a hexamethylbenzene ligand, two chloride ligands and a furfurylamine ligand, the latter coordinating through the amine group. In the crystal, a dimeric structure is obsd. as a result of N-H···Cl interactions between two symmetry-related mols. Crystallog. data and at. coordinates are given. [on SciFinder(R)]