Network Phases with Multiple-Junction Geometries at the Gyroid-Diamond Transition.

A novel phase sequence for the transition from the double diamond to the double gyroid cubic phases via two non-cubic intermediate phases, an orthorhombic Fmmm (O69) phase and a hexagonal P63/m (H176) phase, is reported for specifically designed bolapolyphiles composed of a linear rod-like bistolane core with sticky glycerol ends and two branched central and two linear peripheral side chains. These liquid crystalline (LC) phases represent members of a new class of unicontinuous network phases, formed by longitudinal rod bundles with polar spheres acting as junctions and the alkyl chains forming the continuum around them. In contrast to previously known bicontinuous cubic networks, they combine different junctions with different angles in a common structure, and one of them even represents a triple network instead of the usually found double networks. This provides new perspectives for the design of soft network phases with enhanced structural complexity, inspiring the search for new supramolecular networks, nano-particle arrays, and photonic band-gap materials.

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.

Liquid Organic Frameworks: The Single-Network "Plumber's Nightmare" Bicontinuous Cubic Liquid Crystal.

Novel bolapolyphiles, built of a p-terphenyl or bistolane core with polar glycerol end-groups and two laterally attached n-alkyl or semiperfluoroalkyl chains, form the first "single plumber's nightmare network", the simplest soft-matter cubic phase (Pm3̅m). Its cage-like grid comprises bundles of aromatic rods lying along the cubic unit cell edges, connected by six-way hydrogen-bonded junctions. Side-chains fill the remaining volume of this unique noninterpenetrating liquid-crystalline organic framework.

Controlling Mirror Symmetry Breaking and Network Formation in Liquid Crystalline Cubic, Isotropic Liquid and Crystalline Phases of Benzil-Based Polycatenars.

Spontaneous development of chirality in systems composed of achiral molecules is important for new routes to asymmetric synthesis, chiral superstructures and materials, as well as for the understanding of the mechanisms of emergence of prebiotic chirality. Herein, it is shown that the 4,4'-diphenylbenzil unit is a universal transiently chiral bent building block for the design of multi-chained (polycatenar) rod-like molecules capable of forming a wide variety of helically twisted network structures in the liquid, the liquid crystalline (LC) and the crystalline state. Single polar substituents at the apex of tricatenar molecules support the formation of the achiral (racemic) cubic double network phase with Ia 3 ‾ d symmetry and relatively small twist along the networks. The combination of an alkyl chain with fluorine substitution leads to the homogeneously chiral triple network phase with I23 space group, and in addition, provides a mirror symmetry broken liquid. Replacing F by Cl or Br further increases the twist, leading to a short pitch double gyroid Ia 3 ‾ d phase, which is achiral again. The effects of the structural variations on the network structures, either leading to achiral phases or chiral conglomerates are analyzed.

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.

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 Self-Assembled Bicontinuous Cubic Phase with a Single-Diamond Network.

The first single-diamond cubic phase in a liquid crystal is reported. This skeletal structure with the F d 3 ‾ m space group is formed by self-assembly of bolaamphiphiles with swallow-tailed lateral chains. It consists of bundles of π-conjugated p-terphenyl rods fused into an infinite network by hydrogen-bonded spheres at tetrahedral four-way junctions. We also present a quantitative model relating molecular architecture to the space-filling requirements of six possible bicontinuous cubic phases, that is, the single- and double-network versions of gyroid, diamond, and "plumber's nightmare".

Development of Polar Order by Liquid-Crystal Self-Assembly of Weakly Bent Molecules.

Organic ferroelectrics are of growing importance for multifunctional materials. Here we provide an understanding of the distinct stages of the development of sterically induced polar order in liquid-crystalline (LC) soft matter. Three series of weakly bent molecules derived from 4-cyanoresorcinol as the bent core unit with laterally fluorinated azobenzene wings have been synthesized, and the effects of the position of fluorine substitution, alkyl-chain length, and temperature on the LC self-assembly and polar order were studied. In the LC phases a paraelectric-ferroelectric transition took place as the size of the polar domains gradually increased, thereby crossing a permittivity maximum, similar to inorganic solid-state ferroelectrics. An increase in polar coherence length simultaneously led to a transition from synpolar to antipolar domain correlation in the high-permittivity paraelectric range. Associated with the emergence of polar order was the development of a tilted organization of the molecules and a growing coherence of tilt. This led to a transition from non-tilted via tilt-randomized uniaxial to long-range-tilted biaxial smectic phases, and to surface-stabilized symmetry breaking with the formation of chiral conglomerates and field-induced tilt. Moreover, there is a remarkably strong effect of the position of fluorination; polar order is favored by peripheral core substitution and is suppressed by inside-directed fluorination.

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.

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.

Isothermal Chirality Switching in Liquid-Crystalline Azobenzene Compounds with Non-Polarized Light.

Spontaneous mirror-symmetry breaking is a fundamental process for development of chirality in natural and in artificial self-assembled systems. A series of triple chain azobenzene based rod-like compounds is investigated that show mirror-symmetry breaking in an isotropic liquid occurring adjacent to a lamellar LC phase. The transition between the lamellar phase and the symmetry-broken liquid is affected by trans-cis photoisomerization, which allows a fast and reversible photoinduced switching between chiral and achiral states with non-polarized light.

Dendritic domains with hexagonal symmetry formed by x-shaped bolapolyphiles in lipid membranes.

A novel class of bolapolyphile (BP) molecules are shown to integrate into phospholipid bilayers and self-assemble into unique sixfold symmetric domains of snowflake-like dendritic shapes. The BPs comprise three philicities: a lipophilic, rigid, π-π stacking core; two flexible lipophilic side chains; and two hydrophilic, hydrogen-bonding head groups. Confocal microscopy, differential scanning calorimetry, XRD, and solid-state NMR spectroscopy confirm BP-rich domains with transmembrane-oriented BPs and three to four lipid molecules per BP. Both species remain well organized even above the main 1,2-dipalmitoyl-sn-glycero-3-phosphocholine transition. The BP molecules only dissolve in the fluid membrane above 70 °C. Structural variations of the BP demonstrate that head-group hydrogen bonding is a prerequisite for domain formation. Independent of the head group, the BPs reduce membrane corrugation. In conclusion, the BPs form nanofilaments by π stacking of aromatic cores, which reduce membrane corrugation and possibly fuse into a hexagonal network in the dendritic domains.

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.

2,6-Dibromogallates as a new building block for controlling π-stacking, network formation and mirror symmetry breaking.

Achiral multi-chain (polycatenar) compounds based on the 2,7-diphenyl substituted [1]benzothieno[3,2-b]benzothiophene (BTBT) unit and a 2,6-dibromo-3,4,5-trialkoxybenzoate end group lead to materials forming bicontinuous cubic liquid crystalline phases with helical network structures over wide temperature ranges.

Controlling spontaneous mirror symmetry breaking in cubic liquid crystalline phases by the cycloaliphatic ring size.

Rod-like molecules combining a fork-like triple chain end and a cycloaliphatic apex are introduced as a new design concept for materials with broad ranges of bicontinuous cubic (Cubbi) phases. By ring expansion from n = 4 to 12 a sequence of three Cubbi phases is observed; the achiral double gyroid la3[combining macron]d phase, a chiral "Im3m" phase and an achiral re-entrant la3[combining macron]d phase. The chiral "Im3m" phase is formed if the helical twist between the molecules along the networks is in the range of 8.6°-9.5°, either for the individual compounds or their mixtures.

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.

Spontaneous mirror symmetry breaking in benzil-based soft crystalline, cubic liquid crystalline and isotropic liquid phases.

Benzil (diphenylethane-1,2-dione), which is a long known example for an achiral molecule crystallizing in a chiral space group, can also show mirror symmetry breaking in the fluid state if it is suitably functionalized. For some of the new benzil derivatives even three different subsequent mirror symmetry broken soft matter states with a chiral conglomerate structure can be observed. One is an isotropic liquid, the second one a cubic liquid crystal with a complex network structure and the third is a soft crystalline solid. Chirality develops by helical self-assembly combined with dynamic network formation, thus allowing macroscopic chirality synchronization. These achiral molecules, combining a transiently chiral bent core with multiple alkyl chains, provide a unique link between the mirror symmetry breaking phenomena observed for polycatenar and bent-core mesogens. The homogeneously chiral networks are of interest for application as chiral materials, and as templates for chiral recognition, separation and enantioselective catalysis.

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.

A self-assembled liquid crystal honeycomb of highly stretched (3-1-1)-hexagons.

A new liquid crystalline honeycomb phase is reported, containing highly stretched giant hexagonal cells with two opposing walls spanned by three consecutive end-to-end H-bonded rods, the (3-1-1) hexagons.