Systèmes pi-déficitaires dendritiques à unités périphériques sérinoliques ou diaziniques : synthèse, stéréochimie et propriétés supramoléculaires

par Flavia Adina Popa-Martin

Thèse de doctorat en Chimie organique

Sous la direction de Yvan Ramondenc et de Mircea Darabantu.


  • Résumé

    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.

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La version de soutenance existe sous forme papier

Informations

  • Détails : 1 vol. (228 p.)
  • Notes : Publication autorisée par le jury
  • Annexes : Bibliogr. 191 références

Où se trouve cette thèse\u00a0?

  • Bibliothèque : Université de Rouen. Service commun de la documentation. Section sciences.
  • Disponible pour le PEB
  • Cote : 12/ROUE/S025
  • Bibliothèque : Université de Rouen. Service commun de la documentation. Section sciences site Madrillet.
  • Non disponible pour le PEB
  • Cote : 12/ROUE/S025
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