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A unique gyroid cubic phase has been discovered for a discotic star mesogen with three covalently attached DNA bases. In this cubic Ia3‾d ${Ia\bar{3}d}$ phase, the conjugated core of the mesogens and the thymine pseudo guests self‐assemble in mirror image continuous networks, representing a semiconducting material with three‐dimensional transport pathways. The hole carrier mobilities are found to be in the typical range of poly(phenylenevinylene) scaffolds. This structure is stabilized by a weak hydrogen bonding between the thymine bases and can be switched to a columnar liquid crystal – thermally and by the addition of complementary adenine guests. [ABSTRACT FROM AUTHOR]

Sterically crowded, shape-persistent star mesogens with three oligophenylenevinylene arms provide free space in which Blatter radical guests are incorporated by covalent bonds (esters) or supramolecular interactions (hydrogen bonds). The radical guests transform these compounds to paramagnetic liquid crystalline (LC) materials. The LC molecules are demonstrated to self-assemble into several types of columnar phases, a process that is controlled by the binding mode and the size of the star mesogen cavity. The conjugated scaffold remains stable in the presence of these radicals. Magnetic investigations by means of solid-state VT-EPR and SQUID experiments reveal that these materials are paramagnetic with weak antiferromagnetic interactions. In contrast to the covalent mesogens, the supramolecular systems do not only possess much lower clearing temperatures, but also radical guests exhibit mobility independent of the phase transition leading to soft paramagnetic materials with tunable magnetic properties. [ABSTRACT FROM AUTHOR]

The self‐assembly of umbrella‐shaped mesogens is explored with subphthalocyanine cores and oligo(thienyl) arms with different lengths in the light of their application as light‐harvesting and photoconducting materials. While the shortest arm derivatives self‐assemble in a conventional columnar phase with a single mesogen as a repeating unit, the more extended derivatives generate dimers that pile up into liquid crystalline columns. In contrast to the antiparallel arrangement known from single crystals, the present mesogens align as parallel dimers in polar columnar phases as confirmed by X‐ray scattering, experimental densities, dielectric spectroscopy, second harmonic generation, alignment, and conductivity studies. UV–vis and fluorescence spectroscopies reveal a broad absorption in the visible range and only weak emission of the Q‐band. Thus, these light‐collecting molecules forming strongly polar columnar mesophases are attractive for application in the area of photoconductive materials. [ABSTRACT FROM AUTHOR]

Shape‐persistent conjugated mesogens with oligothiophene arms of different lengths have been synthesized. Such mesogens possess free intrinsic space between their conjugated arms. They form columnar liquid‐crystalline phases, in which the void is filled by dense helical packing in the neat phase similar to an oligo(phenylene vinylene) derivative of equal size. The void can also be compensated by the inclusion of the small acceptor molecule 2,4,7‐trinitrofluorenone. In solution, the acceptor interacts with the core as the largest π‐surface, while in the solid material, it is incorporated between the arms and sandwiched by the star‐shaped neighbours along the columnar assemblies. The TNF acceptors are not nanosegregated from the star‐shaped donors, thus the liquid crystal structure converts to a nano‐reservoir for TNF (endo‐receptor). These host–guest arrangements are confirmed by comprehensive X‐ray scattering experiments and solid‐state NMR spectroscopy. This results in ordered columnar hexagonal phases at high temperatures, which change to helical columnar mesophases or to columnar soft crystals at room temperature. [ABSTRACT FROM AUTHOR]

A small library of shape-persistent, conjugated star-shaped liquid crystals (LCs) with a zinc porphyrin core was successfully synthesized. Different conjugated arms are attached in the meso-positions. The self-assembly is at the limit between liquid crystals and soft crystal phases owing to the space-filling requirement. A model indicates the formation of dimers in double helices. A remarkable mesogen with thiophene linked directly to the porphyrin core generates J-aggregates in solution, which persist in the solid state. In the liquid crystal the J-aggregates disappear but can be reversibly reobtained by solvent treatment. [ABSTRACT FROM AUTHOR]

In the last 50 years, an important aim of molecular and materials design has been the generation of space for the uptake of guest molecules in macrocycles and cryptands, in dendrimers as monomolecular containers, and recently in porous networks like metal-organic and covalent organic frameworks. Such molecular, oligomeric, and polymeric materials can be applied for sensing, separation, catalysis, drug delivery, and gas storage, among others. The common goal is the recognition of molecules and their uptake into and release from an appropriate space. Typically, completely empty space is unfavorable in crystalline materials. Therefore, the elimination of molecules from the cavities is often accompanied by the collapse of the cavities, that is, by a change in the molecular conformation. In contrast to this solid matter, in which the cavities are rationally designed by covalent or coordinative bonds, liquid crystals (LCs) are fluid materials with high molecular mobility. Thus, the proposal of empty space in LCs is certainly a scientific provocation. However, various recent publications on columnar mesophases claim the existence of pores with low electron density or even completely empty space on the basis of X-ray and solid-state NMR studies. Although the latter may be debated, there are many examples in which LCs take up dopants such as polymerizable monomers in disclination lines, perdeuterated chains in the interstices between columns, or electron acceptors to fill mesogens with incommensurate building blocks, which eventually stabilize the LC phases. It seems that in LC science the generation and usage of free space has been studied only occasionally and were lucky discoveries rather than investigations based on rational design. This Account summarizes the research on the formal generation of void in LCs and highlights that rational design of molecules can lead to unconventional mesophases by efficient filling of the provided space, as was shown with shuttlecock mesogens and discotic mesogens related to the concept of complementary polytopic interactions. The topic was recently further developed by the investigation of shape-persistent star mesogens. Despite the formally empty space between their arms, they all form columnar liquid crystals. Such shape-persistent oligo(phenylenevinylene) molecules fill the void and efficiently nanosegregate by helical packing in columns and deformation of the molecular scaffold at the expense of the torsional energy. This inspired us to fill the intrinsic free space by guest molecules either via supramolecular or covalent bonds or just by physical mixing in order to avoid the increase in torsional energy and to stabilize the structure. This strategy led to complex filled liquid-crystalline matter with high structural control and may in the future be used for the design of organic electronic materials that are easily alignable for device applications.