Bent-core liquid crystalline cyanostilbenes: fluorescence switching and thermochromism.

Fluorescent bent-core molecules, bearing one or two cyanostilbene units in the lateral structure and different positions of the cyano group (α- or ß-isomers), are described with the aim of modulating the molecular packing and fluorescence properties. These compounds give rise to a variety of crystal polymorphs and bent-core liquid crystalline phases (SmCP, Colr and B6), offering the unique chance to study the fluorescence properties of the cyanostilbene structure in different phases. Experimental and computational studies elucidate geometrical and electronic properties of these bent-core structures but especially the fluorescence properties (spectral positions, quantum yields and decay curves), in a detailed comparison between diluted solutions, in dichloromethane (DCM) or poly(methylmethacrylate) (PMMA), and condensed phases. Quantum yields as high as 70% have been obtained in some diluted solutions (PMMA) and condensed phases. Remarkably, the quantum yield values depend on the position of the cyano group, being higher for ß- than for the α-isomers due to the higher radiative rates and lower non-radiative rates of the former. The photophysical characterization in the condensed phase focuses on RT studies with solid samples and different processing, and show that, upon aggregation, interactions between the cyanostilbene groups result in changes of the emission spectra and dynamics compared to the diluted systems in DCM and PMMA, giving rise to H-aggregations of varying strength. Furthermore, the compounds exhibit thermochromism, showing a green-yellow fluorescence in the pristine crystalline phase that changes to blue on heating to the liquid crystal phase.

Supramolecular architectures from bent-core dendritic molecules.

Control of the self-assembly of small molecules to generate architectures with diverse shapes and dimensions is a challenging research field. We report unprecedented results on the ability of ionic, bent dendritic molecules to aggregate in water. A range of analytical techniques (TEM, SEM, SAED, and XRD) provide evidence of the formation of rods, spheres, fibers, helical ribbons, or tubules from achiral molecules. The compact packing of the bent-core structures, which promotes the bent-core mesophases, also occurs in the presence of a poor solvent to provide products ranging from single objects to supramolecular gels. The subtle balance of molecule/solvent interactions and appropriate molecular designs also allows the transfer of molecular conformational chirality to morphological chirality in the overall superstructure. Functional motifs and controlled morphologies can be combined, thereby opening up new prospects for the generation of nanostructured materials through a bottom-up strategy.

Liquid-crystalline hybrid materials based on [60]fullerene and bent-core structures.

What a core-ker! By the appropriate combination of promesogenic bent-core structures and the C(60)  unit, lamellar polar liquid-crystal phases were induced. The supramolecular organization of the functional fullerene-based assemblies, the temperature range of the soft phase, the stabilization of the mesophase-like order at room temperature, and the molecular switching under an electric field can be tuned, depending on the molecular structure.

Microfluidics for the rapid and controlled preparation of organic nanotubes of bent-core based dendrimers.

Recently, bent-core molecules have emerged as excellent building blocks for the obtaining of nanostructures in solvents. Herein, we report the use of a coaxial microfluidic system as a promising tool to control the self-assembly of non-conventional bent-core amphiphiles. Moreover, a TEM study to comprehend the hierarchical self-assembly process in solution was carried out. The proposed tool provides both a cost-effective platform to save hard-to-synthesise reagents and a rapid method to screen a plethora of different parameters, i.e., THF/water ratio, residence time, concentration of the amphiphile, temperature and pH. The experiments allowed to test for the first time the suitability of microfluidics for the self-assembly of bent-core molecules, as well as the study of a range of conditions to control the assembly of different nanostructures in a rapid and controlled manner. Additionally, organic nanostructures were combined with gold nanoparticles to prepare nanocomposites with enhanced properties. Both organic and hybrid nanostructures were also obtained in the solid state. These results may inspire scientists working on supramolecular chemistry and bent-core molecules expanding the scope of microfluidic systems for the self-assembly of other low-molecular-weight compounds.

Molecular arrangement in Langmuir and Langmuir-Blodgett films of a mesogenic bent-core carboxylic acid.

A different alternative to previous research on Langmuir and Langmuir-Blodgett (LB) films of bent-core liquid crystals is reported in this work. A bent-shaped molecule wearing a terminal carboxylic group has been used to obtain monomolecular films with their long molecular axis almost perpendicular to the aqueous surface. Langmuir films at the air-liquid interface (pH=9) have been characterized by a combination of surface pressure and surface potential versus area per molecule isotherms, Brewster angle microscopy, and ultraviolet reflection spectroscopy. A condensed phase is reached at surface pressures up to 20 mN x m-1. In this condensed phase, molecules are packed forming H-aggregates with a well-defined molecular orientation. Langmuir films have been transferred onto quartz and silicon substrates and characterized by means of UV-vis spectroscopy and XRR. The transference is Z-type, with a constant deposition of the monolayers. The total LB monolayer film thickness is evaluated to be about 5.8 nm, which is in good agreement with the deduced orientation at the air-liquid interface as well as with the lamellar order observed within the solid obtained by cooling the sample from the mesophase.

TTF-based bent-core liquid crystals.

The synthesis and characterization of bent-core liquid crystals which incorporate TTF groups is reported; different bent-core mesophases are induced depending on the molecular structure and properties derived from their compact packing have been studied.

Self-assembled bent-core side-chain liquid crystalline polymers.

The synthesis of H-bonded bent-core side-chain liquid crystal polymers carried out by two alternative synthetic routes and their properties are reported.

Shell Cross-Linked Polymeric Micelles as Camptothecin Nanocarriers for Anti-HCV Therapy.

A suitable carrier for camptothecin to act as therapy against the hepatitis C virus is presented. The carrier relies on an amphiphilic hybrid dendritic-linear-dendritic block copolymer, derived from pluronic F127 and bis-MPA dendrons, that forms micelles in aqueous solution. The dendrons admit the incorporation of multiple photoreactive groups that allow the clean and effective preparation of covalently cross-linked polymeric micelles (CLPM), susceptible of loading hydrophilic and lipophilic molecules. Cell-uptake experiments using a newly designed fluorophore, derived from rhodamine B, demonstrate that the carrier favors the accumulation of its cargo within the cell. Furthermore, loaded with camptothecin, it is efficient in fighting against the hepatitis C virus while shows lower cytotoxicity than the free drug.

Twist, tilt, and orientational order at the nematic to twist-bend nematic phase transition of 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane: A dielectric, (2)H NMR, and calorimetric study.

The nature of the nematic-nematic phase transition in the liquid crystal dimer 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane (CB9CB) has been investigated using techniques of calorimetry, dynamic dielectric response measurements, and (2)H NMR spectroscopy. The experimental results for CB9CB show that, like the shorter homologue CB7CB, the studied material exhibits a normal nematic phase, which on cooling undergoes a transition to the twist-bend nematic phase (N(TB)), a uniaxial nematic phase, promoted by the average bent molecular shape, in which the director tilts and precesses describing a conical helix. Modulated differential scanning calorimetry has been used to analyze the nature of the N(TB)-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and (2)H magnetic resonance studies have revealed information on the structural characteristics of the recently discovered twist-bend nematic phase. Analysis of the dynamic dielectric response in both nematic phases has provided an estimate of the conical angle of the heliconical structure for the N(TB) phase. Capacitance measurements of the electric-field realignment of the director in initially planar aligned cells have yielded values for the splay and bend elastic constants in the high temperature nematic phase. The bend elastic constant is small and decreases with decreasing temperature as the twist-bend phase is approached. This behavior is expected theoretically and has been observed in materials that form the twist-bend nematic phase. (2)H NMR measurements characterize the chiral helical twist identified in the twist-bend nematic phase and also allow the determination of the temperature dependence of the conical angle and the orientational order parameter with respect to the director.

Breaking the Mold of Discotic Liquid Crystals.

Small molecules of the indene and pseudoazulene type like 1 and 2 form columnar mesophases! These compounds do not possess peripheral flexible chains like conventional columnar liquid crystals. Instead, polarizable chlorine and sulfur atoms, as well as the polar cyano group, function as unusual soft regions between the rigid columns.

Study of an ethylene oxide-terminated bent-core compound: synthesis and Langmuir-Blodgett film structure.

Bent-core compounds have attracted interest due to their unusual supramolecular structures, uncommon physical properties such as ferro- and antiferroelectricity and potential applications in fields such as nonlinear optics. Their incorporation into nanostructured materials, however, needs to be improved in terms of accurate control of the packing and orientation of the molecules in practical structures. Here, we have synthesized a novel bent-core compound bearing a tetraethylene glycol (TEG) chain as the hydrophilic head group and studied its capacity to obtain monomolecular films by means of the Langmuir-Blodgett technique. We developed a synthetic route to the material and studied its behavior in Langmuir and Langmuir-Blodgett films by means of a variety of characterization techniques, including a new model for the interpretation of UV-Vis reflection spectra of bent-core compounds. We found that the new head group, while destroying the formation of bulk mesophases, stabilizes the formation of the monolayer at the air-water interface and allows core-core interactions to dominate film dynamics, thus providing a promising alternative to carboxylic acid head groups.

Study of the photoinduced supramolecular chirality in columnar liquid crystals by infrared and VCD spectroscopies.

IR and VCD spectroscopies are employed to clarify the molecular origins of supramolecular chirality in azobenzene-containing columnar liquid crystals. The different columnar mesomorphic assemblies, Colr and Colh, of an achiral and a chiral propeller-like hydrogen-bonded complex, respectively, are used for this study. The mesomorphic behavior of the achiral complex is studied here for the first time, and the structural parameters of its Colr mesophase are determined by X-ray diffraction. Both complexes bear azobenzene units and this makes it possible to implement photoresponsive columnar architectures, the chirality of which can be induced and modulated by irradiation with 488 nm circularly polarized light (CPL). Thin films of the respective rectangular and hexagonal columnar phases of these complexes have been processed in order to study the IR absorption spectra and the vibrational circular dichroism responses upon irradiation with CPL. These studies allow confirming that the outer part of the columns, consisting on azobenzene groups, is mainly involved in the photoinduced supramolecular chirality, rather than the inner part of the columns where a melamine core is located. This supports a structural model based on the helical disposition of the azobenzene groups along the stacked propeller-like complexes.

Indene and pseudoazulene discotic liquid crystals: a synthetic and structural study.

Several new liquid-crystalline indene and pseudoazulene systems are reported. These molecules give rise to either columnar hexagonal mesophases and/or columnar plastic phases. The unique nature of these compounds stems from their non-classical discotic structure. Although the molecules have rigid aromatic cores, they lack terminal tails and instead the polarizable atoms (S, halogens) or polar groups (CN, CO) act as unusual soft parts. On the basis of many structurally related materials, we conclude that for this type of compound molecular stacking in the solid state is a prerequisite for the appearance of a columnar mesophase, although other intermolecular interactions within the layers are also important in establishing liquid-crystalline order. The behavior reported for these mesomorphic molecules opens up new possibilities in the search for related molecular interactions that might be useful for the construction of supramolecular architectures with particular properties.

SmCP-networked films obtained by in situ photopolymerization of neat reactive banana-shaped liquid crystals.

The synthesis and characterization of reactive banana-shaped compounds have been carried out, and their ability to be photopolymerized in their SmCP mesophase has been assessed. The presence of a SmCP liquid crystalline phase in these compounds has been confirmed by X-ray studies. The polymerization of these molecules has been demonstrated by calorimetric techniques as well as by the preparation and characterization of SmCP-ordered free films that are mechanically stable at room temperature. Furthermore, polymerized films exhibit second harmonic generation activity at room temperature in the absence of an electric field.