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  • Publication
    Accès libre
    Design, Synthesis, and Self-Assembly Behavior of Liquid-Crystalline Bis-[60]Fullerodendrimers
    Russo, Virginie
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    Pieper, Pauline
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    Heinrich, Benoît
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    Donnio, Bertrand
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    Bis-[60]fullerodendrimers were synthesized by assembling [60]fullerene-containing type I (terminal olefin) and type II (a,ß-unsaturated carbonyl olefin) olefins through the olefin cross-metathesis reaction. The synthetic modular approach developed in this study allowed the preparation of mono-[60]fullerodendrimers and their [60]fullerene-free analogues. First- and second-generation poly(aryl ester) dendrons carrying cyanobiphenyl mesogens were used as liquid-crystalline promoters. The liquid- crystalline properties were studied by polarized optical microscopy, differential scanning calorimetry, and small-angle X-ray scattering. In agreement with the nature and structure of the dendrimers, nematic, smectic, and multisegregated lamellar phases were observed. Owing to its versatility and tolerance towards many functional groups, olefin cross-metathesis proved to be a reaction of choice for the elaboration of molecular materials with complex architectures.
  • Publication
    Accès libre
    Olefin Cross-Metathesis: a Versatile Synthetic Reaction for the Design of Janus Liquid Crystals
    Trinh, Thi Minh Nguyet
    ;
    Nguyen, Thanh Tung
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    Kopp, Cyril
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    Pieper, Pauline
    ;
    Russo, Virginie
    ;
    Heinrich, Benoît
    ;
    Donnio, Bertrand
    ;
    Nguyen, Thi Le Anh
    ;
    The olefin cross-metathesis reaction using the second-generation Grubbs catalyst was employed to prepare non-symmetrical thermotropic liquid crystals from various mesomorphic or nonmesomorphic type I and type II olefinic constructs, including linear, chiral, dendritic and ferrocenyl olefins. Smectic C, smectic A and nematic phases, as well as chiral smectic A and chiral nematic phases were observed in agreement with the structure and nature of the mesogens. The olefin cross-metathesis proved to be a valuable chemical reaction in designing dimeric and Janus-like thermotropic liquid crystals built from two different molecular entities.
  • Publication
    Accès libre
    Designing Supramolecular Liquid-Crystalline Hybrids from Pyrenyl-Containing Dendrimers and Arene Ruthenium Metallacycles
    Pitto-Barry, Anaïs
    ;
    Barry, Nicolas P. E
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    Russo, Virginie
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    Heinrich, Benoît
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    Donnio, Bertrand
    ;
    ;
    The association of the arene ruthenium metallacycle [Ru4(p- cymene)4(bpe)2(donq)2][DOS]4 (bpe = 1,2- bis(4-pyridyl)ethylene, donq = 5,8-dioxydo-1,4-naphtoquinonato, DOS = dodecyl sulfate) with pyrenyl-functionalized poly(arylester) dendrimers bearing cyanobiphenyl end- groups is reported. The supramolecular dendritic systems display mesomorphic properties as revealed by polarized optical microscopy, differential scanning calorimetry and small- angle X-ray scattering measurements. The multicomponent nature of the dendrimers and of the corresponding host–guest supramolecules (i.e., end-group mesogens, dendritic core, pyrene unit, aliphatic spacers, and metallacycle) leads to the formation of highly segregated mesophases with a complex multilayered structure due to the tendency of the various constitutive building-blocks to separate in different organized zones. The pyrenyl dendrimers exhibit a multilayered smectic A-like phase, thereafter referred to as LamSmA phase to emphasize this unaccustomed morphology. As for the corresponding Ru4–metallacycle adducts, they self-organize into a multicontinuous thermotropic cubic phase with the Im3¯m space group symmetry. This represents a unique example of liquid- crystalline behavior observed for such large and complex supramolecular host–guest assemblies. Models of their supramolecular organizations within both mesophases are proposed.