Résultat de la recherche
Macrocyclic Effects in the Mesomorphic Properties of Liquid-Crystalline Pillar[5]- and Pillar[6]arenes
Whereas the reaction of 1,4-bis(2-bromoethyloxy)benzene (4) with paraformaldehyde in the presence of BF3·Et2O afforded exclusively the cyclopentameric pillar[5]arene deriv. (5), both cyclopenta- and cyclohexameric macrocycles 5 and 6 were obtained when the reaction of 4 with paraformaldehyde was performed at 45 °C in CHCl3 with FeCl3 as the catalyst. Treatment of compds. 4-6 with sodium azide provided the corresponding polyazides, to which a cyanobiphenyl building block was subsequently grafted to generate model compd. 1, pillar[5]arene 2, and pillar[6]arene 3, bearing two, ten and twelve mesomorphic subunits, resp. The liq.-cryst. and thermal properties of the compds. were investigated by polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). Comparison of the liq.-cryst. properties of macrocycles 2 and 3 with those of 1 revealed the strong influence of the macrocyclic pillar[n]arene core on the mesomorphic properties. Whereas only a monotropic mesophase was obsd. for 1, a broad enantiotropic mesophase was evidenced for both pillar[n]arene derivs. [on SciFinder(R)]
Amphiphilic and mesomorphic fullerene-based dendrimers
Growing attention is currently devoted to large dendritic structures for applications in nanotechnol. and materials science. In this respect, the incorporation of such compds. into thin ordered films appears to be an important issue. One of the most widely pursued approaches to structurally ordered dendrimer assemblies was the prepn. of Langmuir films at the air-water interface. We report on the case of a diblock globular fullerene-based dendrimer and show that peripheral substitution of the dendrimer with hydrophobic chains on one hemisphere and hydrophilic groups on the other provides the required hydrophobic/hydrophilic balance allowing the formation of stable Langmuir films. A second approach was to consider the case of fullerene contg. dendrimers terminated by mesogenic groups such as cyanobiphenyl subunits. Whatever the generation is, up to the fourth one, all these compds. exhibit a well-defined liq. cryst. smectic A phase. The mol. organization within the smectic layers is monolayered or bilayered depending on the generation. For the smallest dendrimers, the organization is mainly governed by the size of the fullerene moiety, whereas for the higher ones, it is governed by the interactions between the terminal mesogenic groups. These two approaches appear particularly interesting for functional groups such as fullerenes, which are not well adapted to be organized in nanoscale architectures. The present study shows that fullerenes can indeed be introduced into different types of ordered structure when they were chem. adequately modified. 3',3''-(Methanoxymethano[1,3]benzenomethanoxymethano)-3'H,3''H-dicyclop ropa[1,9:3,15][5,6]fullerene-C60-Ih-3',3''-dicarboxylic acid. [on SciFinder(R)]
Self-organisation of dodeca-dendronized fullerene into supramolecular discs and helical columns containing a nanowire-like core
Twelve chiral and achiral self-assembling dendrons have been grafted onto a [60]fullerene hexa-adduct core by copper-catalyzed alkyne azide "click" cycloaddition. The structure adopted by these compounds was determined by the self-assembling peripheral dendrons. These twelve dendrons mediate the self-organisation of the dendronized [60]fullerene into a disc-shaped structure containing the [60]fullerene in the centre. The fullerene-containing discs self-organise into helical supramolecular columns with a fullerene nanowire-like core, forming a 2D columnar hexagonal periodic array. These unprecedented supramolecular structures and their assemblies are expected to provide new developments in chiral complex molecular systems and their application to organic electronics and solar cells.
Fullerene-containing dendrimers: synthesis and properties
A review. The aim of this review is not to give an exhaustive review on fullerene-contg. dendrimers but to present examples to illustrate the current state-of-the-art of fullerene chem. for the development of new functional dendrimers. [on SciFinder(R)]
Liquid-crystalline fullerene-oligophenylenevinylene conjugates
Functionalization of C60-oligophenylenevinylene derivs. with a cyanobiphenyl-terminated dendromesogen leads to new donor-acceptor systems with liq.-cryst. properties. [on SciFinder(R)]
Building liquid crystals from the 5-fold symmetrical pillar[5]arene core
Comparison of the liquid-crystalline properties of a pillar[5]arene core functionalized with 10 mesogenic cyanobiphenyl units with those of a corresponding model compound revealed the strong influence of the macrocyclic pillar[5]arene core on the mesomorphic properties.
Building liquid crystals from the 5-fold symmetrical pillar[5]arene core
Comparison of the liq.-cryst. properties of a pillar[5]arene core functionalized with 10 mesogenic cyanobiphenyl units with those of a corresponding model compd. revealed the strong influence of the macrocyclic pillar[5]arene core on the mesomorphic properties. [on SciFinder(R)]
Amphiphilic fullerene-cholesterol derivatives: synthesis and preparation of Langmuir and Langmuir-Blodgett films
Amphiphilic fullerene bis-adducts 11 and 14 contg. two and four cholesterol moieties, resp., were prepd. starting from the corresponding bis-malonate derivs. In a systematic study, their spreading behavior at the air-H2O interface was compared to that of bis-adduct 6 with no polar head-group. Compared to 6, for which some three-dimensional aggregation occurs, the polar head-group in 11 and 14 is responsible for an attractive interaction with the aq. subphase, forcing the mols. towards the H2O surface into a two-dimensional arrangement. Even if homogeneous Langmuir films were obtained with both 11 and 14, only the films of 14 show a reversible compression/expansion behavior. This suggests that, by increasing the no. of cholesterol subunits, the encapsulation of the C-sphere in its addend is more efficient, thus preventing fullerene-fullerene interactions and aggregation phenomena. The Langmuir films of 11 and 14 were also efficiently transferred onto hydrophilic quartz slides, yielding Langmuir-Blodgett films. [on SciFinder(R)]