Nematic phases of bent-core mesogens
TL;DR: In this article, a temperature dependent stepwise transition from cybotactic nematic phases to different types of non-polar and tilted smectic phases (SmC(I) and SmC(II)) is observed with a mesophase composed of elongated, but not yet fused cybactic clusters (CybC) as an intermediate state of this transition.
Abstract: Bent-core mesogens derived from 4-cyanoresorcinol with terminal alkyl chains have been synthesized and investigated by polarizing microscopy, XRD and electro-optical methods. Short chain compounds have exclusively nematic phases which can be cooled to ambient temperature. These nematic phases are similar to ordinary nematic phases with only nearest neighbour correlation (N) whereas long chain compounds form SmC-type cybotactic clusters and these cybotactic nematic phases (NcybC) can be regarded as strongly fragmented SmC phases. The chain length dependent as well as temperature dependent structural transition from N to NcybC is continuous and associated with a change of the position and intensity of the small angle scattering in the XRD patterns. Moreover, a temperature dependent stepwise transition from cybotactic nematic phases to different types of non-polar and tilted smectic phases (SmC(I) and SmC(II)) is observed with a mesophase composed of elongated, but not yet fused cybotactic clusters (CybC) as an intermediate state of this transition. This improves the understanding of the nature and special properties of the nematic phases formed by bent-core molecules as well as their transition to smectic phases and it paves the way to new materials with spontaneous or field-induced biaxial nematic phases at ambient temperatures.
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TL;DR: New exciting soft-matter structures distinct from the usually observed nematic, smectic, and columnar phases are presented, including multicompartment and cellular structures, periodic and quasiperiodic arrays of spheres, and new emergent properties, such as ferroelctricity and spontaneous achiral symmetry-breaking.
Abstract: 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.
456 citations
TL;DR: An overview of the current state of research in the field of biaxial nematic liquid crystalline materials is given in this paper, where the major theoretical concepts are outlined, including the classification to different symmetries, the importance of cooperativity and cluster formation for the development of BN order and the conditions for the establishment of field induced and spontaneous BN in nematic phases.
Abstract: An overview over the current state of research in the field of biaxial nematic liquid crystalline materials is given. After a short introduction, providing some general aspects and summarizing the classical approaches, the main part focuses on recent developments of new concepts for designing biaxial nematics. First, the major theoretical concepts are outlined, including the classification to different symmetries, the importance of cooperativity and cluster formation for the development of biaxial order and the conditions for the establishment of field induced and spontaneous biaxiality in nematic phases. These new concepts also require the re-evaluation of the tools used for the identification of phase biaxiality, which are discussed briefly. In the second part, recent progress in the design of potential biaxial nematic materials, especially focussing on bent-core molecules with nematic phases, is reported and, finally, comparisons with phase biaxiality as observed in smectic liquid crystals are made.
299 citations
25 Jun 2013
TL;DR: A comprehensive review of the main research directions and results can be found in this article, where the authors describe the properties of smectic nano clusters often observed in BCNs, and discuss rheological properties that reveal unusually large viscosities and small twist and bend elastic constants.
Abstract: Bent-core (BC) materials that form nematic liquid crystals (BC nematics (BCNs)) are known only since 2000, but since then they have been intensively studied. In this review we give a comprehensive summary of the main research directions and results. After discussing representative examples of molecules making BCNs, we review theoretical predictions and experimental findings about macroscopic symmetries, such as chirality of achiral and chiral molecules, tetrahedratic symmetry and phase biaxiality versus uniaxiality. Then we describe the properties of smectic nano clusters often observed in BCNs, and discuss rheological properties that reveal unusually large viscosities and small twist and bend elastic constants. Finally, we focus on the electric properties of BCNs, such as dielectric and ferroelectric properties, electroconvection (EC) and electromechanical effects.
148 citations
TL;DR: Progress in the understanding of a new dynamic mode of symmetry breaking, based on chirality synchronisation of transiently chiral molecules in isotropic liquids and in bicontinuous cubic, columnar, smectic and nematic liquid crystalline phases is discussed.
Abstract: Spontaneous mirror symmetry breaking is an efficient way to obtain homogeneously chiral agents, pharmaceutical ingredients and materials. It is also in the focus of the discussion around the emergence of uniform chirality in biological systems. Tremendous progress has been made by symmetry breaking during crystallisation from supercooled melts or supersaturates solutions and by self-assembly on solid surfaces and in other highly ordered structures. However, recent observations of spontaneous mirror symmetry breaking in liquids and liquid crystals indicate that it is not limited to the well-ordered solid state. Herein, progress in the understanding of a new dynamic mode of symmetry breaking, based on chirality synchronisation of transiently chiral molecules in isotropic liquids and in bicontinuous cubic, columnar, smectic and nematic liquid crystalline phases is discussed. This process leads to spontaneous deracemisation in the liquid state under thermodynamic control, giving rise to long-term stable symmetry-broken fluids, even at high temperatures. These fluids form conglomerates that are capable of extraordinary strong chirality amplification, eventually leading to homochirality and providing a new view on the discussion of emergence of uniform chirality in prebiotic systems.
140 citations
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1,660 citations
TL;DR: An overview on the recent developments in the field of liquid crystalline bent-core molecules (so-called banana liquid crystals) is given in this article, 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.
Abstract: 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.
753 citations
TL;DR: In this article, structural and properties of liquid crystalline phases formed by bent-core molecules are reviewed and the most attractive properties of this new class of liquid crystals are in polarity and chirality, despite being formed from achiral molecules.
Abstract: 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.
713 citations
TL;DR: Polarized microscopy and conoscopy indicate that liquid crystal mesogens based on a nonlinear oxadiazole unit that exhibit nematic phases near 200 degrees C are biaxial nematics, and unambiguous and quantitative evidence for biaXiality is achieved using 2H NMR spectroscopy.
Abstract: We have synthesized liquid crystal (LC) mesogens based on a nonlinear oxadiazole unit that exhibit nematic phases near $200\text{ }\ifmmode^\circ\else\textdegree\fi{}\mathrm{C}$ Polarized microscopy and conoscopy indicate that these LCs are biaxial nematics Unambiguous and quantitative evidence for biaxiality is achieved using $^{2}\mathrm{H}$ NMR spectroscopy ``2D powder'' spectra, obtained by rotating $^{2}\mathrm{H}$-labeled samples about an axis perpendicular to the magnetic field at $\ensuremath{\sim}200\text{ }\text{ }\mathrm{Hz}$, yield phase biaxiality parameters of $\ensuremath{\sim}01$ when coupled with rigorous and proven simulations
534 citations
IBM1
533 citations