Formation of columnar liquid crystals on the basis of unconventional triazine-based dendrimers by the C3-symmetric approach

Two series of unconventional triazine-based dendrimers with C(2) symmetry and C(3) symmetry were prepared. The newly prepared C(3)-symmetrical dendrimers were characterized by (1)H and (13)C NMR spectroscopy, mass spectrometry, and elemental analysis. Differential scanning calorimetry, polarizing microscopy, and powder XRD showed that the C(3)-symmetrical dendrimers display columnar liquid-crystalline phases during thermal treatment, but the C(2)-symmetrical dendrimers were not observed to behave correspondingly. The molecular conformations of C(3)- and C(2)-symmetrical dendrimers were obtained by computer simulation with the MM2 model of the CaChe program in the gas phase. The simulation results reasonably explain the different mesogenicities of C(3)- and C(2)-symmetric dendrimers. This new strategy should be applicable to other types of unconventional dendrimers with rigid frameworks for displaying columnar liquid-crystalline behavior.     

Star-shaped oligobenzoates: non-conventional mesogens forming columnar helical mesophases

Star-shaped mesogens with a phloroglucinol or a trimesic acid core and oligobenzoate arms with up to five repeating units have been synthesised. These non-conventional mesogens form various columnar mesophases over a broad temperature range. The liquid-crystal phases were characterised by optical microscopy, differential scanning calorimetry, X-ray diffraction, dilatometry and solid-state NMR spectroscopy. In addition to the high-temperature hexagonal columnar phases, the columnar self-assemblies undulate upon cooling and consequently form higher-ordered body-centred orthorhombic columnar 3D structures. A model of E-shaped folded conformers helically displaced along the columns is proposed. Helical preorganisation in the hexagonal phase precedes the transition to the low-temperature phases. Space filling and nano-segregation compete in the self-organisation process, thus aliphatic chains and the polar oligobenzoate scaffold are not perfectly separated in these star-shaped mesogens.     

Nanostructured columnar and cubic liquid-crystalline assemblies consisting of unconventional rigid mesogens based on triphenylmethanes

Liquid-crystalline (LC) molecules of unconventional shapes that form columnar and micellar cubic structures have been synthesized using triarylmethyl moieties as building blocks. The molecules have bowl- and dumbbell-shape. Despite the rigidity and bulkiness of the triarylmethyl moieties, the molecules form columnar and micellar cubic LC phases. The bowl-shaped molecules containing one triarylmethyl moiety show LC phases. The LC temperature ranges of the dumbbell-shaped molecules containing two triarylmethyl moieties connected by rigid rods are wider than those of bowl-shaped molecules containing one triarylmethyl moiety. The UV-vis spectroscopy of the dumbbell-shaped molecules having a terphenyl moiety reveals that the terphenyl moieties aggregate in the mesophase.     

New switchable columnar liquid crystals

Penta- and hexa-substituted phenanthrenes and penta-substituted benzo[c]-phenanthrenes have been synthesized; these exhibit columnar phases and are electrically switchable when bearing chiral side chains. The liquid crystalline and electro-optical properties are described. A strong tri-state switching behaviour is observed with the phenanthrene derivatives. A helical phase structure, responsible for this switching behaviour, is proposed and the possible mechanism of the columnar phase switching process is discussed.     

Sequences in dendrons and dendrimers

Sequential incorporation of a variety of functional groups forms the basis for specificity in biomacromolecules. Introduction of such diversity and sequencing ability in artificial macromolecules is fundamentally interesting. In this paper, three different synthetic approaches have been used to build dendrons and dendrimers in which all the monomer units are different from each other. The synthetic strategies described in this paper involve the use of (i) an ABB(p) monomer, (ii) an ABB' monomer, and (iii) an ABB(m) monomer. The complementarity and the versatility of these synthetic approaches should render them useful for a variety of applications.     

First carbohydrate liquid crystals of columnar structure

S, S-Dialkylacetals of aldoses, tripodal in structure and recently synthesized in large numbers by three groups, do not exhibit thermotropically a smectic, but a columnar hexagonal mesophase (Hx) as we have proved by X-ray diffraction. The molecular organization in this mesophase is comparable with a similar one known for phasmidic molecules. These various multiols, although different in stereo-chemistry, form only one type of hydrogen-bonded disc-shaped multimer. Its mesophase structure is made up of about five molecules placed in columns with a skeleton of hydrogen-bridged sugar parts surrounded by thioalkyl groups in the periphery. Since three 6-deoxy sugar dithioacetals were shown to be non-thermomesomorphic the terminal hydroxyl function is essential for this molecular arrangement which seems not to be true for missing ones in the inner part of a sugar chain, as we have found in one case.     

Star-shaped supramolecular ionic liquid crystals based on pyridinium salts

Series of novel star-shaped liquid crystals containing [1,1?-biphenyl]-4,4?-diyl diisonicotinate mesogens with various counterions (Br^?, B-SO₃^?,C-SO₃^?,H₂PO₄^?, BF₄^?) have been synthesized and characterized, which display a nematic phase. The molecular structures of the liquid crystals, thereof consisting of rod-like mesogens linked together by different long alkyl spacers to a small disc-like core of central benzene-1,3,5-triyl triisonicotinate, have been fully characterized by ¹H NMR. Their thermal and supramolecular organization behaviours have been studied by combining polarized optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. These investigations showed that the mesophase temperature range increased with increasing alkyl chain length and the clearing point decreased with increase of anion size. These star-shaped liquid crystals have a long and ordered molecular structure, the electron delocalization of the π-π stacking conjugation effect and the electrostatic attraction of ionic make them have good ferroelectric properties and ionic conductivity properties. The interest in preparing ionic liquid crystal with a nematic phase lies in the technological applications as it is well known that the nematic phase has the highest fluidity of all liquid crystalline phases and hence the possibility to align it by applying an external electric/magnetic field, commonly used in electro-optical devices.     

Core-halogenated, helical-chiral triphenylene-based columnar liquid crystals

It is shown that chlorination and even bromination of the mesogenic hexahexyloxytriphenylene 1 can take place at the sterically congested tetracyclic core delivering the respective monohalogenated, sevenfold substituted enantiotropic mesogens 3 and 4 in 32 and 17% yields, respectively, giving mesophases over greater temperature ranges. Miscibility tests among all mesogenic compounds of this study prove formation of the columnar hexagonal type of phase. The steric and electronic effects of those substituents, different from the six equal alkoxy groups, on the mesophase are discussed in detail. In our hands and to our surprise, the sterically hindered acceptor (nitro or halogeno) substituents of 2, 3, or 4 could not be replaced by an alkylthio group in nucleophilic aromatic substitution reactions using the aprotic polar solvent DMEU. Semi-empirical calculations on numerous hexaethers with one or two substituents, e.g. halogens or others, in one of the three bay regions of the triphenylene core reveal that these molecules are helically deformed due to the crowding in the molecule. In this new case of atropisomerism, the 1,12-disubstituted derivatives should offer the possibility of resolution into enantiomers and, therefore, of studying disc-like mesomorphic compounds possessing for the first time the origin of chirality within their molecular centre.     

Core-halogenated,helical-chiral triphenylene-based columnar liquid crystals

It is shown that chlorination and even bromination of the mesogenic hexahexyloxytriphenylene 1 can take place at the sterically congested tetracyclic core delivering the respective monohalogenated, sevenfold substituted enantiotropic mesogens 3 and 4 in 32 and 17% yields, respectively, giving mesophases over greater temperature ranges. Miscibility tests among all mesogenic compounds of this study prove formation of the columnar hexagonal type of phase. The steric and electronic effects of those substituents, different from the six equal alkoxy groups, on the mesophase are discussed in detail. In our hands and to our surprise, the sterically hindered acceptor (nitro or halogeno) substituents of 2, 3, or 4 could not be replaced by an alkylthio group in nucleophilic aromatic substitution reactions using the aprotic polar solvent DMEU. Semi-empirical calculations on numerous hexaethers with one or two substituents, e.g. halogens or others, in one of the three bay regions of the triphenylene core reveal that these molecules are helically deformed due to the crowding in the molecule. In this new case of atropisomerism, the 1,12-disubstituted derivatives should offer the possibility of resolution into enantiomers and, therefore, of studying disc-like mesomorphic compounds possessing for the first time the origin of chirality within their molecular centre.     

Luminescent columnar liquid crystals based on tristriazolotriazine

Five discotic molecules comprising a tris[1,2,4]triazolo[1,3,5] triazine core were designed and synthesized to obtain luminescent and charge-transporting columnar liquid crystalline materials. With the exception of one compound containing terminal hydroxyl groups all compounds presented a wide thermal range and stable columnar liquid crystalline phase, characterized by differential scanning calorimetry, polarized optical microscopy, and X-ray diffraction (XRD) techniques. The phase formation appeared to be associated to some extent with interdigitation of the alkoxy and benzylalkoxy portion, as suggested by the XRD results. All compounds have a strong blue luminescence in solution and solid phase. At the temperature at which the compounds enter in the mesophase the luminescence decreases significantly. This result suggests that entrance into the Col(h) phase is accompanied by a better π-stacking of the peripheral phenyl rings compared to the solid phase, consistent with the intramolecular distances (3.5 ?) observed in the XRD analysis. These compounds based on tristriazolotriazine are quite robust with good optical and thermal properties for application as solid state emitters, and we anticipate that they may provide an interesting alternative to other discotic molecules based on N-heterocycles, which generally present a high-temperature Col(h) phase.     

Nanomaterials of triazine-based dendrons: convergent synthesis and their physical studies

[structure: see text] Without employing protection and deprotection processes, two series of triazine-based dendrons were efficiently prepared by a convergent method and fully characterized; their physical properties, including acidic, thermal, electrical, and optical stabilities were also studied.     

Snowflake-like dendrimers via site-selective synthesis of dendrons

[structure: see text] Snowflake-shaped dendrimers were prepared via site-selective synthesis of dendrons, where an attachment of encapsulating dendritic branches and an extension of phenylacetylenic units were alternatively manipulated on the structure of AB(2) (diethyltriazeno for A and bromo for B) substituted diphenylacetylene using a combination of Suzuki and Sonogashira cross-coupling reactions.     

Highly congested liquid crystal structures: dendrimers, dendrons, dendronized and hyperbranched polymers

In this tutorial review we describe some studies concerning liquid crystal dendritic polymers. We have chosen to present several representative examples that illustrate the diverse kinds of LC dendritic structures, namely: dendrimers, dendrons, dendronized polymers and hyperbranched polymers. We review their synthesis, mesogenic properties and the way that they are arranged to form supramolecular liquid crystal assemblies.     

Modular peripheral functionalization of thiophene dendrons and dendrimers

A series of thiophene dendrons and dendrimers with peripheral functional groups were designed and synthesized. Two methodologies using thiophene dendrons and dendrons as synthetic building blocks, namely, (1) periphery functionalization; (2) a combination of focal and periphery functionalization have been demonstrated.     

Amphiphilic carbohydrate-based mesogens incorporating structural features of calamitic liquid crystals

Abstract

Several examples of liquid-crystalline carbohydrate derivatives incorporating a carbocyclic ring in the side chain are reported and the influence of structural variations discussed. The mesophase observed for all compounds described is smectic A and the mesophase stability is strongly affected by the linking unit between the carbocyclic and carbohydrate moieties.     

Novel supramolecular columnar liquid crystals based on thiosemicarbazides

Novel liquid crystal materials based on 3,4-di-n-alkoxybenzoylthiosemicarbazides (3a–h, n = 5–10, 12, 14) were synthesised. The mesomorphic properties of these compounds were characterised and studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. Compound 3a did not show mesomorphic properties; 3b shows a monotropic hexagonal columnar (Col_h) phase. Compounds 3c–h display an enantiotropic Col_h phase. The mesomorphic properties were found to be dependent on the length of alkoxy side chains. In N,N-dimethylformamide solution, all the compounds displayed a room temperature emission with λ_max at 361–332 nm. A thermogravimetric analysis also was performed.     

Viologen-based redox-active ionic liquid crystals forming columnar phases

Viologens possessing three alkoxy chains at each terminal self-organize into columnar liquid-crystalline phases through nanophase segregation and electrostatic interactions. These viologens are redox-active and susceptible to two consecutive electrochemical reductions.     

Amphiphilic carbohydrate-based mesogens incorporating structural features of calamitic liquid crystals

Several examples of liquid-crystalline carbohydrate derivatives incorporating a carbocyclic ring in the side chain are reported and the influence of structural variations discussed. The mesophase observed for all compounds described is smectic A and the mesophase stability is strongly affected by the linking unit between the carbocyclic and carbohydrate moieties.     

Structural factors controlling the self-assembly of columnar liquid crystals

A series of disc-shaped molecules were prepared by the condensation of 1,2-diamines with 2,3,6,7-tetrakis(hexyloxy)phenanthrene-9,10-dione to investigate the relationship between changes in molecular structure and the self-assembly of columnar liquid crystalline phases. A comparison of compounds with different core sizes indicated that molecules with larger aromatic cores had a greater propensity to form columnar phases, as did compounds substituted with electron-withdrawing groups. In contrast, molecules with electron-donating substituents were nonmesogenic. The clearing temperature of columnar phases increased linearly with the electron-withdrawing ability of the substituents, as quantified by Hammett sigma-values. The observed trends can be rationalized in terms of the strength of pi-pi interactions between aromatic cores in the liquid crystalline phases and suggest that both electrostatic interactions and dispersion forces play important roles in the self-assembly of these materials.