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Three naphthorosarins, antiaromatic expanded porphyrins bearing different meso substituents (NRos 1–3), designed to self-assemble into columnar liquid crystalline (LC) structures, were synthesized and characterized using polarized optical microscopy (POM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), as well as supporting computational calculations. The substituents were found to play a crucial role in modulating the LC behaviour.

The synthesis, supramolecular self-assembly and structural characterization of a new family of tetraethylene oxide (TEG)-based bent-core compounds and their 1/1 lithium-containing complexes are reported. TEG-based bent-core amphiphiles, even joining the TEG/Li+ tandem, are suitable building-blocks to achieve supramolecular nanostructures, in some cases showing chiral features from achiral molecules either in the mesophase or in solvents. The thermal and liquid crystal behavior of these materials studied by polarizing optical microscopy and X-ray diffraction confirmed that Li-based materials stabilized polar smectic C and helical nanofilament-type mesophases, in contrast to the non-liquid crystalline pure TEG-compounds. Alternatively, both the pure amphiphiles and the lithium-doped materials self-assemble into physical gels in non-polar solvents, displaying three-dimensional networks composed of long fibers with lamellar molecular organizations as shown by transmission electron microscopy and X-ray diffraction. Interestingly, biphenyl- and azobenzene-based bent core amphiphiles aggregate in solvent into chiral nanostructured morphologies with supramolecular trends comparable to their molecular arrangement in their liquid crystalline phases.

We have carried out a spectroscopic study on a prototype ferroelectric nematic material (RM734) doped with a non-polar chiral compound. The mixture presents two chiral nematic phases, one conventional (N*) and the other polar (NF*), whose behaviours under electric fields E are totally different. On the one hand, the N* phase shows a single reflection band if E is not very high, while fields perpendicular to the helix of a few V/mm are already sufficient to produce multiple bands in the NF* phase. On the other hand, the pitch of the NF* phase grows notably on increasing fields, however remaining practically constant in the N* phase. Both effects have been explained in terms of the different type of interaction with E in each phase (ferroelectric in NF* and dielectric in N*). We argue that the NF* phase behaves as a photonic material with multiple gaps tunable by small fields, which presents important potentials for applications. A study of the bandgaps has been carried out through the analysis of the dispersion relation of the optical eigenmodes in the NF* phase under field. Finally, an example of the potentials of the NF* phase within the field of nonlinear optics is briefly presented.

Materials that exhibit high nonlinear optical (NLO) susceptibilities are considered as promising candidates for a wide range of photonic and electronic applications. Here, we argue that the ferroelectric nematic (NF) materials have sufficient potentialities to become materials for the next-generation of NLO devices. We have carried out a study of the efficiency of optical second-harmonic generation in a prototype NF material, finding a nonlinear susceptibility of 5.6 pm.V−1 in the transparent regime, one of the highest ever reported in ferroelectric liquid crystals. Given the fact that the studied molecule was not specifically designed for NLO applications, we conclude there is still margin to obtain NF materials with enhanced properties that should allow their practical use.

Computational and experimental studies unravel the structural and electronic properties of a novel supramolecular liquid crystal built through a hierarchical assembly process resulting in an H‐bonded melamine rosette decorated with peripheral triphenylenes. The six‐fold symmetry of the mesogen facilitates the formation of a highly organized hexagonal columnar mesophase stable at room temperature. X‐ray diffraction and electron density maps confirm additional intra‐ and intercolumn segregation of functional subunits, and this paves the way for 1D charge transport. Indeed, hole mobility has been measured and found to be higher than for related mesogens. DFT calculations of HOMO and LUMO levels and parameters such as reorganization energy and transfer integral of the rosette structure have been achieved, and not only validate the columnar organization but also establish the way it translates into a favorable electronic architecture and molecular orbital interactions to promote charge carrier mobility.

A novel approach to ambipolar semiconductors based on hydrogen-bonded complexes between a star-shaped tris(triazolyl)triazine and triphenylene-containing benzoic acids is described. The formation of 1:3 supramolecular complexes was evidenced by different techniques. Mesogenic driving forces played a decisive role in the formation of the hydrogen-bonded complexes in the bulk. All of the complexes formed by nonmesogenic components gave rise to hexagonal columnar (Col) liquid crystal phases, which are stable at room temperature. In all cases, X-ray diffraction experiments supported by electron density distribution maps confirmed triphenylene/tris(triazolyl)triazine segregation into hexagonal sublattices and lattices, respectively, as well as remarkable intracolumnar order. These highly ordered nanostructures, obtained by the combined supramolecular H-bond/columnar liquid crystal approach, yielded donor/acceptor coaxial organization that is promising for the formation of ambipolar organic semiconductors with high mobilities, as indicated by charge transport measurements.

The self-assembly of axial dipolar subphthalocyanine molecules in the presence of electric fields leads to uniaxially oriented columnar liquid crystalline materials that exhibit permanent polarization.

A polar response in a lyotropic columnar nematic material is reported. The material accommodates bowl-shaped molecules with strong axial dipole moments in column segments without head-to-tail invariance. Optical second-harmonic-generation methods confirm that the nematic columns align unidirectionally under an applied electric field and the material develops remnant macroscopic polarization observable for hours. The switching takes place by a flip of the columns.

The synthesis and characterization of three bent-rod dimers are reported. Very long flexible spacers that include methylene units and either a phenyl ring or a triazole moiety as connecting structures join the bent- and rod-promesogenic cores. Polarizing microscopy, modulated differential scanning calorimetry, X-ray diffraction at variable temperature and dielectric measurements have been performed to establish the mesophase behaviour of the dimers. The results show a complex supramolecular organization for this kind of flexible dimer in the mesophase. Interestingly, the length and the chemical nature of the flexible linking spacers condition the liquid crystalline properties of these novel compounds. Additionally, it has been found that the chemical structure of the rod-like core plays a key role in determining the kind of mesophase, either nematic or lamellar, formed by these materials. © 2014 the Partner Organisations.

Three series of bent-shaped compounds containing the 1,2,3-triazole ring in the central core of the molecule have been prepared by the most extended >click chemistry> reaction, the copper-catalyzed azide-alkyne cycloaddition (CuAAC). This research demonstrates the versatility of this synthetic approach with the aim of achieving innovative compact supramolecular organizations. The appropriate combination of the 1,2,3-triazole synthon linked either to a methylene unit (series M) or to a methylenoxycarbonyl block (series MC) has allowed the induction of a variety of non-classical bent-core liquid crystal phases versus the classic mesophases promoted by 1,4-diphenyl-1,2,3- triazole derivatives (series T). Through a suitable selection of common lateral structures connected by >click chemistry> both the transition temperatures and mesomorphism, ranging from lamellar to columnar or B4-like supramolecular liquid crystalline organizations, can be tuned. © The Royal Society of Chemistry 2012.

The changes in the x-ray diffraction diagram induced by an electric field have been studied in four bent-core liquid crystals. Two of the compounds present columnar B1 phases and the other two show dark conglomerate (DC) structures. In the B1 materials the electric field gives rise to switchable phases whose diffraction pattern is that of the smectic C polar (SmCP) phase. In the DC structures the positions of the Bragg reflections remain essentially unaltered, but in one of the compounds the peaks become narrower under field, indicating that the correlation length of the smectic order increases. A slight enhancement of the smectic spacing is found in the DC phases upon field application.

The smectic A (SmA) phase of a V-shaped mesogen with a molecular bending angle of 60° was studied. According to X-ray measurements, the molecules are arranged with the ‘bow-string’ direction parallel to the smectic layer. This point was confirmed by birefringence analysis and the result is compatible with a non-polar structure. A detailed study of the (001) smectic layer reflection versus temperature was also carried out to determine the smectic translational order parameter. The results indicate that the material presents a high degree of translational order. In addition, the electric field response of the material was studied by means of second harmonic generation. This technique turned out to be highly sensitive to small structural distortions due to the V-shape of the constituent molecules.

Three bent-core liquid-crystal compounds presenting the unusual columnar B1 to tilted polar smectic (Sm-CP or B2) phase transition are studied through small-angle x-ray diffraction on aligned samples. The well-established character of the smectic phase helps to characterize the structural changes during the transition. A mechanism for this transition is proposed, which accounts for the low enthalpy usually observed in this process. The B1 phase is found to possess a great degree of lamellarization, with pseudosmectic ferroelectric layers along the crystallographic (11) planes. As a consequence of these observations a distribution of the block polarizations in the columnar structure is proposed.

We present a structural study of the mesophases of three achiral bent-core compounds with azo and azoxy bonds. The study is based on textures observation and small-angle X-ray diffraction. It is found that the materials exhibit columnar and tilted smectic mesophases. Optical second-harmonic generation measurements are performed on aligned samples of one of the compounds, and the whole second-order susceptibility tensor is determined. Finally, some simple aspects of the photoisomerization of the materials are examined.