The rhombic honeycomb - a new mode of self-assembly in liquid crystalline soft matter.

Rod-like liquid crystalline (LC) polyphilic compounds with a linear oligo(phenyleneethynylene) core, sticky glycerol groups at each end and two long alkyl side chains (C20-C32) at opposite sides form rhombic honeycombs with inner angles around 60/120°, occurring between triangular and square tiling patterns.

Tetrahedral Liquid-Crystalline Networks: An A15-Like Frank-Kasper Phase Based on Rod-Packing.

The Pm 3 ‾ n cubic and other low-symmetry Frank-Kasper phases are known to be formed by soft spheres, ranging from metals to block copolymer micelles and colloidal nanoparticles. Here, we report a series of X-shaped polyphiles composed of sticky rods and two non-symmetric branched side-chains, which self-assemble into the first example of a cubic liquid-crystalline phase representing a tetrahedral network of rods with a Pm 3 ‾ n lattice. It is the topological dual to the Weaire-Phelan foam, being the Voronoi tessellation of the A15 sphere packing, from which this network is obtained by Delaunay triangulation.

Emergence of uniform tilt and π-stacking in triangular liquid crystalline honeycombs.

The synclinic tilted organization of specifically designed polyphilic oligo(p-phenylene ethynylene) rods in cylindrical shells around triangular prismatic cells on the <5 nm scale leads to a new kind of liquid crystalline honeycomb composed of helical shells with alternating helix sense. Core fluorination at the outer ring modifies the core-core interactions, thus resulting in triangular arrays with face-to-face π-stacking along the honeycomb.

Different Modes of Deformation of Soft Triangular Honeycombs at the Sub-5 nm Scale.

Patterning on the sub-5 nm length scale is a contemporary challenge for further miniaturization of microelectronic circuits. Here, the first soft self-assembled triangular patterns are reported showing transitions between regular and two different kinds of isosceles (acute and obtuse angled) triangles on this length scale, formed by liquid crystalline honeycombs of polyphilic block molecules involving a fluorinated oligo(para-phenylene ethynylene) core. The type of formed triangular pattern depends on the degree and position of fluorination and on temperature. They are the first soft honeycombs combining tilted and nontilted organizations in a uniform nanostructure, where the tilted molecules in only one or two sides of the triangular prismatic cells dominate the shape and the size of the morphology.

Liquid Organic Frameworks: A Liquid Crystalline 8-Connected Network with Body-Centered Cubic Symmetry.

Liquid state self-assembly is important for the understanding of the complex structures developed in abiogenesis and biogenesis as well as for numerous potential technological applications. Herein we report the first body-centered cubic liquid crystalline phase with 8-connected network topology and open octahedral network structure. It is formed by dynamic soft self-assembly of X-shaped polyphiles with oligo(para-phenylene-ethynylene) cores. The π-conjugated rods with perfluorinated inner benzene rings form networks conjoined by eight-way junctions, which are formed by nano-segregated spheres involving hydrogen-bonded polar end groups, while the branched aliphatic chains at opposite sides of the cores fill the continuum. This novel cubic phase is based on the I-WP minimal surface separating the frameworks of polyaromatic cores from the most disordered chain segments. It can also be considered as a dense sphere packing. Such liquid organic frameworks, representing hybrids of sphere packings and networks could be of interest for organic photonics and other technologies.

A periodic dodecagonal supertiling by self-assembly of star-shaped molecules in the liquid crystalline state.

Molecular tessellations are known in solid state systems and their formation is often induced or supported by a periodic surface lattice. Here we discover a complex tessellation on the 10 nm length scale, spontaneously formed in the highly dynamic liquid crystalline state. It is composed of overlapping dodecagonal supertiles combining prismatic cells with triangular and square cross sections. This complex honeycomb occurs between a triangular honeycomb at high and a square at low temperature, being opposite to the sequence expected for a thermal expansion of the side chains in the prismatic cells. Formation of the supertiles is supported by the segregation of alkyl chains with different length. The emergent behaviour of this complex soft matter structure is demonstrated, and intriguing connections between self-assembly on surfaces, in liquid crystals, and in block copolymers are drawn. Moreover, the tessellation represents a close approximant of the elusive columnar liquid quasicrystal with dodecagonal symmetry.

Stereochemical Rules Govern the Soft Self-Assembly of Achiral Compounds: Understanding the Heliconical Liquid-Crystalline Phases of Bent-Core Mesogens.

A series of bent-shaped 4-cyanoresorcinol bisterephthalates is reported. Some of these achiral compounds spontaneously form a short-pitch heliconical lamellar liquid-crystalline phase with incommensurate 3-layer pitch and the helix axis parallel to the layer normal. It is observed at the paraelectric-(anti)ferroelectric transition, if it coincides with the transition from random to uniform tilt and with the transition from anticlinic to synclinic tilt correlation of the molecules in the layers of the developing tilted smectic phase. For compounds with long chains the heliconical phase is only field-induced, but once formed it is stable in a distinct temperature range, even after switching off the field. The presence of the helix changes the phase properties and the switching mechanism from the naturally preferred rotation around the molecular long axis, which reverses the chirality, to a precession on a cone, which retains the chirality. These observations are explained by diastereomeric relations between two coexisting modes of superstructural chirality. One is the layer chirality, resulting from the combination of tilt and polar order, and the other one is the helical twist evolving between the layers. At lower temperature the helical structure is replaced by a non-tilted and ferreoelectric switching lamellar phase, providing an alternative non-chiral way for the transition from anticlinic to synclinic tilt.

Emergence of tilt in square honeycomb liquid crystals.

First liquid crystalline phases with tilted organization of rod-like aromatics in a square honeycomb structure were discovered. The developing tilt is temperature, chain length and chain volume dependent, and has a dramatic effect on the optical properties, occasionally leading to an inversion of birefringence. The observed effects of chain branching on tilt contributes to a general understanding of lateral chain engineering in tailoring the self-assembly of π-conjugated molecular rods.

Transition from nematic to gyroid-type cubic soft self-assembly by side-chain engineering of π-conjugated sticky rods.

A sequence of liquid crystalline phases, involving cybotactic nematics, a lamellar phase, bicontinuous cubics and triangular honeycombs, was observed for oligo(phenylene ethynylene) based X-shaped bolapolyphiles with two long lateral alkyl chains and sticky ends provided by glycerol groups. In the cubic phase with Ia3[combining macron]d lattice - which is tailored by alkyl chain engineering - the aromatic cores are organized on the gyroid minimal surface in 3D curved layers of almost parallel aligned π-conjugated rods. It is shown that this type of cubic phase is a general mode of soft self-assembly of X-shaped bolapolyphiles at the cross-over from the (long or short range) lamellar to the triangular honeycomb-like organization. Cubic phase formation is found only in a narrow range with respect to temperature and chain-length for the non-fluorinated compounds and in much wider ranges for related core-fluorinated molecules.

Formation of a Cubic Liquid Crystalline Nanostructure with π-Conjugated Fluorinated Rods on the Gyroid Minimal Surface.

Bicontinuous cubic phases are of significant importance for numerous applications, for example, for the crystallization of membrane proteins, as photonic materials and as templates for porous silica. A new variant of bicontinuous cubic liquid crystalline phase with Ia3‾ d lattice is reported herein for X-shaped bolapolyphiles. It was shown that in this class of compounds, cubic-phase induction can be achieved by proper aromatic core fluorination; in addition, the first cubic phases having π-conjugated oligo(phenylene ethynylene) rods on the gyroid minimal surface were obtained. These new structures composed of 3D folded layers of parallel arranged π-conjugated rods should allow charge transport in all three dimensions, which is of interest for organic semiconductor applications.

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behaviour. Part 1: Transition between Amphiphilic and Polyphilic Self-Assembly in the Bulk.

Polyphilic self-assembly leads to compartmentalization of space and development of complex structures in soft matter on different length scales, reaching from the morphologies of block copolymers to the liquid crystalline (LC) phases of small molecules. Whereas block copolymers are known to form membranes and interact with phospholipid bilayers, liquid crystals have been less investigated in this respect. Here, series of bolapolyphilic X-shaped molecules were synthesized and investigated with respect to the effect of molecular structural parameters on the formation of LC phases (part 1), and on domain formation in phospholipid bilayer membranes (part 2). The investigated bolapolyphiles are based on a rod-like π-conjugated oligo(phenylene ethynylene) (OPE) core with two glycerol groups being either directly attached or separated by additional ethylene oxide (EO) units to both ends. The X-shape is provided by two lateral alkyl chains attached at opposite sides of the OPE core, being either linear, branched, or semiperfluorinated. In this report, the focus is on the transition from polyphilic (triphilic or tetraphilic) to binary amphiphilic self-assembly. Polyphilic self-assembly, i.e., segregation of all three or four incorporated units into separate nano-compartments, leads to the formation of hexagonal columnar LC phases, representing triangular honeycombs. A continuous transition from the well-defined triangular honeycomb structures to simple hexagonal columnar phases, dominated by the arrangement of polar columns on a hexagonal lattice in a mixed continuum formed by the lipophilic chains and the OPE rods, i.e., to amphiphilic self-assembly, was observed by reducing the length and volume of the lateral alkyl chains. A similar transition was found upon increasing the length of the EO units involved in the polar groups. If the lateral alkyl chains are enlarged or replaced by semiperfluorinated chains, then the segregation of lateral chains and rod-like cores is retained, even for enlarged polar groups, i.e., the transition from polyphilic to amphiphilic self-assembly is suppressed.

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behavior. Part 2: Domain Formation by Self-Assembly in Lipid Bilayer Membranes.

Supramolecular self-assembly of membrane constituents within a phospholipid bilayer creates complex functional platforms in biological cells that operate in intracellular signaling, trafficking and membrane remodeling. Synthetic polyphilic compounds of macromolecular or small size can be incorporated into artificial phospholipid bilayers. Featuring three or four moieties of different philicities, they reach beyond ordinary amphiphilicity and open up avenues to new functions and interaction concepts. Here, we have incorporated a series of X-shaped bolapolyphiles into DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) bilayers of giant unilamellar vesicles. The bolapolyphiles consist of a rod-like oligo(phenylene ethynylene) (OPE) core, hydrophilic glycerol-based headgroups with or without oligo(ethylene oxide) expansions at both ends and two lateral alkyl chains attached near the center of the OPE core. In the absence of DPPC and water, the compounds showed thermotropic liquid-crystalline behavior with a transition between polyphilic and amphiphilic assembly (see part 1 in this issue). In DPPC membranes, various trends in the domain morphologies were observed upon structure variations, which entailed branched alkyl chains of various sizes, alkyl chain semiperfluorination and size expansion of the headgroups. Observed effects on domain morphology are interpreted in the context of the bulk behavior (part 1) and of a model that was previously developed based on spectroscopic and physicochemical data.

Effects of molecular chirality on self-assembly and switching in liquid crystals at the cross-over between rod-like and bent shapes.

A bent-core compound derived from a 4-cyanoresorcinol core unit with two terephthalate based rod-like wings and carrying chiral 3,7-dimethyloctyloxy side chains has been synthesized in racemic and enantiomerically pure form and characterized by polarizing microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical investigations to study the influence of molecular chirality on the superstructural chirality and polar order in lamellar liquid crystalline phases. Herein we demonstrate that the coupling of molecular chirality with superstructural layer chirality in SmCsPF domain phases (forming energetically distinct diastereomeric pairs) can fix the tilt direction and thus stabilize synpolar order, leading to bistable ferroelectric switching in the SmC* phases of the (S)-enantiomer, whereas tristable modes determine the switching of the racemate. Moreover, the mechanism of electric field induced molecular reorganization changes from a rotation around the molecular long axis in the racemate to a rotation on the tilt-cone for the (S)-enantiomer. At high temperature the enantiomer behaves like a rod-like molecule with a chirality induced ferroelectric SmC* phase and an electroclinic effect in the SmA'* phase. At reduced temperature sterically induced polarization, due to the bent molecular shape, becomes dominating, leading to much higher polarization values, thus providing access to high polarization ferroelectric materials with weakly bent compounds having only "weakly chiral" stereogenic units. Moreover, the field induced alignment of the SmCsPF(()*()) domains gives rise to a special kind of electroclinic effect appearing even in the absence of molecular chirality. Comparison with related compounds indicates that the strongest effects of chirality appear for weakly bent molecules with a relatively short coherence length of polar order, whereas for smectic phases with long range polar order the effects of the interlayer interfaces can override the chirality effects.

Spontaneous helix formation in non-chiral bent-core liquid crystals with fast linear electro-optic effect.

Liquid crystals (LCs) represent one of the foundations of modern communication and photonic technologies. Present display technologies are based mainly on nematic LCs, which suffer from limited response time for use in active colour sequential displays and limited image grey scale. Herein we report the first observation of a spontaneously formed helix in a polar tilted smectic LC phase (SmC phase) of achiral bent-core (BC) molecules with the axis of helix lying parallel to the layer normal and a pitch much shorter than the optical wavelength. This new phase shows fast (∼30 µs) grey-scale switching due to the deformation of the helix by the electric field. Even more importantly, defect-free alignment is easily achieved for the first time for a BC mesogen, thus providing potential use in large-scale devices with fast linear and thresholdless electro-optical response.

Development of polar order and tilt in lamellar liquid crystalline phases of a bent-core mesogen.

A new bent-core mesogen combining a 4-cyanoresorcinol unit with two terephthalate based rod-like wings and terminated by two long alkyl chains, was synthesized and investigated by DSC, XRD, optical, electrooptical and dielectric methods. A series of liquid crystalline phases in the unique sequence SmA-SmA(P)-SmCPR-(M1/SmCPα)-SmCsPA-SmCPA-SmCaPA, mainly distinguished by the degree and mode of correlation of tilt and polar order, was observed. The development of polar order is associated with the emergence of a small tilt (<10°). With decreasing temperature the tilt changes from random (SmA) via synclinic to anticlinic, while the coherence length of the polar domains grows. This small tilt gives rise to an only weak layer coupling which is in competition with the polar coupling and this leads to new modes of self assembly in lamellar phases of bent-core mesogens, among them the SmCPR and the SmCPα phases. The SmCPR phase is an only slightly tilted biaxial smectic phase with randomized polar order and the SmCPα phase is a slightly tilted and antiferroelectric switching, but uniaxial smectic phase. For this phase a regular change of the in-plane polarization vector between the layers by an angle between >0° and <90° is proposed.