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Deschenaux, Robert

Nom
Deschenaux, Robert
Affiliation principale
Fonction
Professeur ordinaire
Email
Robert.Deschenaux@unine.ch
Identifiants
https://libra.unine.ch/handle/123456789/384

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  • Publication
    Accès libre
    Photophysical, electrochemical, and mesomorphic properties of a liquid-crystalline [60]fullerene–peralkylated ferrocene dyad
    (2008)
    Campidelli, Stéphane
    ;
    Séverac, Marjorie
    ;
    Scanu, David
    ;
    Deschenaux, Robert 
    ;
    Vázquez, Ester
    ;
    Milic, Dragana
    ;
    Prato, Maurizio
    ;
    Carano, Maurizio
    ;
    Marcaccio, Massimo
    ;
    Paolucci, Francesco
    ;
    Rahman, G. M. Aminur
    ;
    Guldi, Dirk M.
    Two fullerene–peralkylated ferrocene derivatives were synthesized: (1) a liquid-crystalline dyad (compound 1) was obtained by introduction of nonamethyl ferrocene into a liquid-crystalline fullerene derivative and (2) a reference compound (compound 2) was synthesized by attachment of nonamethyl ferrocene to a fulleropyrrolidine. The liquid-crystalline dyad displayed an enantiotropic smectic A phase from 57 to 155 °C. Oxidation and reduction processes were investigated by cyclic voltammetry, and were in agreement with the electrochemical characteristics of the redox-active units (peralkylated ferrocene, fullerene, dendrimer). Photoinduced electron transfer from ferrocene derivative to fullerene was identified.
  • Publication
    Accès libre
    Liquid−Crystalline Janus-Type Fullerodendrimers Displaying Tunable Smectic−Columnar Mesomorphism
    (2007)
    Lenoble, Julie
    ;
    Campidelli, Stéphane
    ;
    Maringa, Natacha
    ;
    Donnio, Bertrand
    ;
    Guillon, Daniel
    ;
    Yevlampieva, Natalia
    ;
    Deschenaux, Robert 
    Janus-type liquid−crystalline fullerodendrimers were synthesized via the 1,3-dipolar cycloaddtition of two mesomorphic dendrons and C60. By assembling poly(aryl ester) dendrons functionalized with cyanobiphenyl groups, displaying lamellar mesomorphism, with poly(benzyl ether) dendrons carrying alkyl chains, which display columnar mesomorphism, we could tailor by design the liquid−crystalline properties of the title compounds as a function of each dendron size. The liquid−crystalline properties were examined by polarized optical microscopy, differential scanning calorimetry, and X-ray diffraction. Depending on the dendrimer generations, smectic (SmC and/or SmA phases) or columnar (Colr-c2mm or Colr-p2gg phases) mesomorphism was obtained. The supramolecular organization is governed by (1) the adequacy of the cross-sectional area of the dendrons, (2) the microsegregation of the dendrimer, (3) the deformation of the dendritic core, and (4) the dipolar interactions between the cyanobiphenyl groups. Comparison of the mesomorphic properties of two fullerodendrimers with those of model compounds (fullerene-free analogues) indicated that the C60 unit does not influence the type of mesophase that is formed. Molecular properties determined in solution (permanent dipole moment, specific dielectric polarization, molar Kerr constant) confirm that microsegregation persists in solution and strengthen the models proposed for the structure of the mesophases.
  • Publication
    Accès libre
    Dendritic liquid-crystalline fullerene–ferrocene dyads
    (2006-02-25)
    Campidelli, Stéphane
    ;
    Pérez, Laura
    ;
    Rodríguez-López Julián
    ;
    Barberá, Joaquín
    ;
    Langa, Fernando
    ;
    Deschenaux, Robert 
    First- and second-generation ferrocene-based dendrimers, fullerene and a second-generation liquid-crystalline poly(arylester) dendrimer carrying four cyanobiphenyl units were assembled to elaborate polyfunctional materials displaying mesomorphic and electronic properties. The targeted compounds gave rise to enantiotropic smectic A phases and organized into bilayer structures within the smectic layers. Cyclic voltammetry investigations revealed oxidation and reduction processes in agreement with the presence of both ferrocene and fullerene units. Finally, strong quenching of the fluorescence was obtained for the fullerene–ferrocene dyads suggesting efficient elecron transfer from the ferrocene-based dendrimer to fullerene.
  • Publication
    Accès libre
    Encoding calamitic mesomorphism in thermotropic lanthanidomesogens
    (2006)
    Terazzi, Emmanuel
    ;
    Bocquet, Bernard
    ;
    Campidelli, Stéphane
    ;
    Donnio, Bertrand
    ;
    Guillon, Daniel
    ;
    Deschenaux, Robert 
    ;
    Piguet, Claude
    Peripheral cyanobiphenyl dendrimers impose a microphase organization compatible with smectic mesomorphism, in which the bulky nine-coordinate lanthanide core is located between the decoupled mesogenic sublayers made up of parallel cyanobiphenyl groups.
  • Publication
    Accès libre
    An optically-active liquid-crystalline hexa-adduct of [60]fullerene which displays supramolecular helical organization
    (2006)
    Campidelli, Stéphane
    ;
    Brandmüller, Torsten
    ;
    Andreas Hirsch
    ;
    Saez, Isabel M.
    ;
    Goodby, John W.
    ;
    Deschenaux, Robert 
    Polyaddition of mesogenic moieties to C60 were found to yield chiral supermolecular nanoparticles which exhibit iridescent helical chiral nematic phases.
  • Publication
    Accès libre
    A dendritic fullerene–porphyrin dyad
    (2006)
    Campidelli, Stéphane
    ;
    Deschenaux, Robert 
    ;
    Swartz, Angela
    ;
    Rahman, G. M. Aminur
    ;
    Guldi, Dirk M.
    ;
    Milic, Dragana
    ;
    Vázquez, Ester
    ;
    Prato, Maurizio
    We describe the synthesis, characterization and photophysical properties of a fullerene derivative whose structure includes a Zn-porphyrin and a second generation liquid-crystalline (LC) dendrimer. The size of the fullerene and porphyrin units with respect to the size of the LC dendrimer prevents the formation of liquid-crystalline phases. However, this system gives interesting photoinduced electron transfer phenomena. Compound 1 has been investigated by steady state and time resolved fluorescence as well as transient absorption spectroscopy in polar and apolar solvents. We demonstrate that the fluorescence of the porphyrin unit in 1 is quenched compared to the Zn-tetraphenylporphyrin used as reference. Femto- and picosecond transient absorption permit to identify the formation of a radical ion pair while nanosecond experiments allowed the determination of the charge recombination lifetimes.
  • Publication
    Accès libre
    Liquid-Crystalline Bisadducts of [60]Fullerene
    (2006)
    Campidelli, Stéphane
    ;
    Vázquez, Ester
    ;
    Milic, Dragana
    ;
    Lenoble, Julie
    ;
    Atienza Castellanos, Carmen
    ;
    Sarova, Ginka
    ;
    Guldi, Dirk M.
    ;
    Deschenaux, Robert 
    ;
    Prato, Maurizio
    A second-generation cyanobiphenyl-based dendrimer was used as a liquid-crystalline promoter to synthesize mesomorphic bisadducts of [60]fullerene. Liquid-crystalline trans-2, trans-3, and equatorial bisadducts were obtained by condensation of the liquid-crystalline promoter, which carries a carboxylic acid function, with the corresponding bisaminofullerene derivatives. A monoadduct of fullerene was also prepared for comparative purposes. All the compounds gave rise to smectic A phases. An additional mesophase, which could not be identified, was observed for the trans-2 derivative. The supramolecular organization of the monoadduct derivative is governed by steric constraints. Indeed, for efficient space filling, adequacy between the cross-sectional areas of fullerene (∼100 Å2) and of the mesogenic groups (∼22−25 Å2 per mesogenic group) is required. As a consequence, the monoadduct forms a bilayered smectic A phase. The supramolecular organization of the bisadducts is essentially governed by the nature and structure of the mesogenic groups and dendritic core. Therefore, the bisadducts form monolayered smectic A phases. The title compounds are promising supramolecular materials as they combine the self-organizing behavior of liquid crystals with the properties of fullerene.
  • Publication
    Accès libre
    Dendritic liquid-crystalline fullerene–ferrocene dyads
    (2006)
    Campidelli, Stéphane
    ;
    Pérez, Laura
    ;
    Rodríguez-López Julián
    ;
    Barberá, Joaquín
    ;
    Langa, Fernando
    ;
    Deschenaux, Robert 
    First- and second-generation ferrocene-based dendrimers, fullerene and a second-generation liquid-crystalline poly(arylester) dendrimer carrying four cyanobiphenyl units were assembled to elaborate polyfunctional materials displaying mesomorphic and electronic properties. The targeted compounds gave rise to enantiotropic smectic A phases and organized into bilayer structures within the smectic layers. Cyclic voltammetry investigations revealed oxidation and reduction processes in agreement with the presence of both ferrocene and fullerene units. Finally, strong quenching of the fluorescence was obtained for the fullerene–ferrocene dyads suggesting efficient elecron transfer from the ferrocene-based dendrimer to fullerene.
  • Publication
    Accès libre
    Supramolecular Fullerene Materials:  Dendritic Liquid-Crystalline Fulleropyrrolidines
    (2005)
    Campidelli, Stéphane
    ;
    Lenoble, Julie
    ;
    Barberá, Joaquín
    ;
    Paolucci, Francesco
    ;
    Marcaccio, Massimo
    ;
    Paolucci, Demis
    ;
    Deschenaux, Robert 
    [60]Fullerene-containing liquid-crystalline dendrimers were synthesized from the first to the fourth generation by applying the 1,3-dipolar cycloaddition reaction from a mesomorphic dendritic-type aldehyde derivative, sarcosine (N-methylglycine) or glycine and C60. The cyanobiphenyl unit was used as a liquid-crystalline promoter. With the exception of the first-generation fullerene dendrimer, which was found to be nonmesomorphic, all fullerene-based dendrimers gave rise to a smectic A phase. The liquid-crystalline fullerenes led to two different supramolecular organizations within the smectic layers:  for the second-generation dendrimers, the molecules are oriented in a head-to-tail fashion within the layers; for each molecule the cyanobiphenyl units point in the same direction. For the dendrimers of third and fourth generations, the dendritic core extends laterally, parallel to the layer planes; the mesogenic units are oriented above and below the dendritic core. For the aldehyde precursors, only one organization inside the layers was obtained, similar to the one observed for the third and fourth fullerene-based dendrimers. Cyclic voltametry investigations displayed several one-electron and multielectron reduction processes; no significant interaction in the ground state between the fullerene and the dendrimer was noticed. The title compounds showed the typical electrochemical stability of fulleropyrrolidines.
  • Publication
    Accès libre
    Liquid-crystalline fullerene–ferrocene dyads
    (2004)
    Campidelli, Stéphane
    ;
    Vázquez, Ester
    ;
    Milic, Dragana
    ;
    Prato, Maurizio
    ;
    Barberá, Joaquín
    ;
    Guldi, Dirk M.
    ;
    Marcaccio, Massimo
    ;
    Paolucci, Demis
    ;
    Paolucci, Francesco
    ;
    Deschenaux, Robert 
    The 1,3-dipolar cycloaddition reaction was used to assemble fullerene, ferrocene and a second-generation liquid-crystalline cyanobiphenyl-based dendrimer. The targeted compound displayed an enantiotropic smectic A phase from 40 to 135 °C. The d-layer spacing was determined by X-ray diffraction, and was found to be independent of temperature with a value of 95 Å. Molecular modeling and structural considerations suggested partial bilayer organization of the mesogenic molecular units within the smectic layers. Oxidation or reduction processes of the basic components (ferrocene, fullerene, dendrimer) were investigated by electrochemical techniques, and were in agreement with the structure. Photoinduced electron transfer from ferrocene to fullerene was identified, most likely with a “through space” mechanism.