An overview on the recent developments in the field of liquid crystalline bent-core molecules (so-called banana liquid crystals) is given. After some basic issues, dealing with general aspects of the systematisation of the mesophases, development of polar order and chirality in this class of LC systems and explaining some general structure–property relationships, we focus on fascinating new developments in this field, such as modulated, undulated and columnar phases, so-called B7 phases, phase biaxiality, ferroelectric and antiferroelectric polar order in smectic and columnar phases, amplification and switching of chirality and the spontaneous formation of superstructural and supramolecular chirality.

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Bent-core liquid crystals: polar order, superstructural chirality and spontaneous desymmetrisation in soft matter systems

Structures and properties of liquid crystalline phases formed by bent-core molecules are reviewed. At least eight phases designated as B1–B8 have been found, being unambiguously distinguished from phases formed by usual calamitic molecules due to a number of remarkable peculiarities. In addition to B1–B8 phases, smectic A-like phases and biaxial nematic phases formed by bent-core molecules are also reviewed. The most attractive aspects of this new class of liquid crystals are in polarity and chirality, despite being formed from achiral molecules. The bent-core mesogens are the first ferroelectric and antiferroelectric liquid crystals realized without introducing chirality. Spontaneous chiral deracemization at microscopic and macroscopic levels occurs and is controllable. Moreover, achiral bent-core molecules enhance system chirality. The interplay between polarity and chirality provides chiral nonlinear optic effects. Further interesting phenomena related to polarity and chirality are also reviewed.

https://iopscience.iop.org/article/10.1143/JJAP.45.597/pdf

Bent-Core Liquid Crystals: Their Mysterious and Attractive World

https://orbilu.uni.lu/bitstream/10993/20503/1/Lagerwall%20%26%20Scalia%202012.pdf

A new era for liquid crystal research: Applications of liquid crystals in soft matter nano-, bio- and microtechnology

Since the discovery of the liquid-crystalline state of matter 125 years ago, this field has developed into a scientific area with many facets. This Review presents recent developments in the molecular design and self-assembly of liquid crystals. The focus is on new exciting soft-matter structures distinct from the usually observed nematic, smectic, and columnar phases. These new structures have enhanced complexity, including multicompartment and cellular structures, periodic and quasiperiodic arrays of spheres, and new emergent properties, such as ferroelctricity and spontaneous achiral symmetry-breaking. Comparisons are made with developments in related fields, such as self-assembled monolayers, multiblock copolymers, and nanoparticle arrays. Measures of structural complexity used herein are the size of the lattice, the number of distinct compartments, the dimensionality, and the logic depth of the resulting supramolecular structures.

Development of structural complexity by liquid-crystal self-assembly.

Liquid crystals are finding increasing applications in a wide variety of fields including liquid-crystal display technology, materials science, bioscience, etc., apart from acting as prototype self-organizable supramolecular soft materials and tunable solvents. Recently, keeping in pace with topical science, liquid crystals have entered into the fascinating domains of nanoscience and nanotechnology. This tutorial review describes the recent and significant developments in liquid-crystal nanoscience embracing contemporary nanomaterials such as nanoparticles, nanorods, nanotubes, nanoplatelets, etc. The dispersion of zero-, one- and two-dimensional nanomaterials in liquid crystals for the enhancement of properties, liquid-crystalline phase behavior of nanomaterials themselves, self-assembly and alignment of nanomaterials in liquid-crystalline media, and the synthesis of nanomaterials by using liquid crystals as ‘templates’ or ‘precursors’ have been highlighted and discussed. It is almost certain that the ‘fourth state of matter’ will play more prevalent roles in nanoscience and nanotechnology in the near future. Moreover, liquid-crystal nanoscience reflects itself as a beautiful demonstration of the contemporary theme “crossing the borders: science without boundaries”.

Liquid-crystal nanoscience: an emerging avenue of soft self-assembly

Two columnar phases of bent-core molecules have been observed, with a two-dimensional (2D) structure modulated in the plane perpendicular to the direction of the spontaneous polarization vector. The phases are switchable under an applied electric field, contrary to the commonly observed 2D modulated ${B}_{1}$ phase. These new phases are built from broken smectic layers with orthogonal or tilted molecules. The evidence for a 3D structure in which the density modulations along and perpendicular to the spontaneous polarization vector co-exists is also given.

Bent-core liquid crystals forming two- and three-dimensional modulated structures.

The polycatenar bent-shaped molecules are able to form columnar phases with column stratum built of few molecules, arranged in coplanar or conelike geometry. In the latter case, the phase becomes axially polar, with electric spontaneous polarization reorientable in the electric field by flipping the cone axis. The phase is antiferroelectric; in the plane perpendicular to columns, the ferroelectric hexagonal order exists, but the columns are broken along the z direction and the polarization direction alternates between the blocks.

Axially polar columnar phase made of polycatenar bent-shaped molecules.

Spontaneous formation of smectic and columnar structures was observed when spherical gold nanoparticles were functionalized with mesogenic thiols (see layered structure and X-ray pattern of a sample in smectic phase). The particle ordering is stimulated by softening of the interparticle potential and flexibility for deformation of the grafting layer.

Liquid-Crystalline Phases Made of Gold Nanoparticles†

Most mesogens formed by banana-shaped molecules exhibit liquid-like smectic phases. Here we present the synthesis and properties of homologous series of derivatives of resorcinol and 2,6-disubstituted pyridine. One of these classes of bent-core molecules displays the nematic phase.

Nematic phase formed by banana-shaped molecules

The columnar phases made of polycatenar molecules with bent shaped mesogenic core are studied. The polar order in this system is associated with the change of the column building blocks from flat discs (Colh phase) into cones (ColhPA phase), which allows for axial polarization of the columns. The nature of Colh and ColhPA phase transition changes from the first order for short homologues to continuous for the longest one. This can be attributed to decreasing intercolumnar interactions due to broadening of the columnar scaffold made of partially melted terminal alkyl chains. Decrease of intercolumnar interactions is also responsible for strong increase of pretranstional fluctuations in the Colh phase. The mesophase observed for longest homologues is reminiscent of relaxor phase observed for solid crystals.

Joanna Matraszek

Papers

Bent-core liquid crystals forming two- and three-dimensional modulated structures.

Axially polar columnar phase made of polycatenar bent-shaped molecules.

Liquid-Crystalline Phases Made of Gold Nanoparticles†

Nematic phase formed by banana-shaped molecules

Polar order in columnar phase made of polycatenar bent-core molecules.