Thèse de doctorat en Chimie organique
Soutenue en 2012
à Rouen en cotutelle avec l'Université Babes-Bolyai, Cluj-Napoca , dans le cadre de École doctorale normande de chimie (Caen) , en partenariat avec Chimie organique et bioorganique : Réactivité et Analyse (Mont-Saint-Aignan, Seine-Maritime) (laboratoire) .
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Our work described in this Ph. D. Thesis concerns the synthesis, the stereochemical analysis and the supramolecular properties of new π-deficient dendritic systems having C-2 substituted 2-aminopropane-1,3-diols (serinols) or diazines as peripheral units. The first chapter presents the synthesis, the fluorescence and two-photon absorption properties of new G-0, G-1 dendritic compounds incorporating diazine moieties. The convergent synthesis of the dendritic structures are based on Sonogashira cross-coupling reactions. The first type of compounds contains a trisubstituted aromatic cycle, pyrimidine, benzene and triphenylamine as core. The acetylene linkers connect the core to the peripheral units : the pyridazine cycle with donating groups (dibutylamino, methoxy) or the pyrimidine cycle with methyl groups. The second type of structures have aromatic cycles with donating groups (dimethylamino, dibutylamino, methoxy) linked by E-ethylene linkers at diazine moieties as trivalent branched cells. These structures present interesting fluorescence properties with quantum yields up to 60%, large Stokes shifts and two-photon absorption cross-section values up to 450 GM. The second chapter describes the iterative chemoselective amination of cyanuric chloride, the structure and dynamic behaviour of new G-2 dendritic N-substituted-2,4,6-triamino-s-triazines (melamines) containing C-2 substituted 2-aminopropane-1,3-diols (serinols) in tandem with the ethylene ketal of 4-piperidone or only the 2-methyl-2aminopropanol as peripheral units. These dendritic structures have the s-triazine cycle as branched cells and two types of linkers, the piperazine and a central one, the 4,4'-bipiperidine. The stereochemistry of rotational phenomena occurring about the newly created C(s-triazine)-N<(exocyclic) partial double bonds for all these dendritic building-blocks is discussed. The structure as gradual increasing of molecular size of these compounds is studied by NMR spectroscopy, DFT calculation and AFM imaging.