Liquid‐Crystalline Triangle Honeycomb Formed by a Dithiophene‐Based X‐Shaped Bolaamphiphile

Cheng, Xiaonong; Dong, Xian; Wei, Guanghui; Prehm, Marko; Tschierske, Carsten

doi:10.1002/ange.200903247

Cited by 14 publications

(11 citation statements)

References 26 publications

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“…As a consequence of the thinner walls, effectively more space is left available for the lateral chains inside the cells. Hence, honeycombs with smaller cells could be achieved by using two short lateral chains instead of only one chain with the same total volume [41].…”

Section: X-shaped Polyphiles and Multi-colour Tilingsmentioning

confidence: 99%

“…Hence, the number of colours was further increased to five by the different mixing Figure 9. Dependence of honeycomb wall thickness on the type of polyphile, shown for the case of a square cylinder phase; (a) double wall structure of T-shaped polyphiles; (b) single wall cylinders formed by X-shaped polyphiles [41,60].…”

Section: X-shaped Polyphiles and Multi-colour Tilingsmentioning

confidence: 99%

“…As longer rods provide more space inside the cylinders, the number of walls in the cross section of the cylinder must be reduced, i.e. moving clockwise around the diagram in figure 5 [7,41,43,44]. Especially pentagonal and hexagonal cylinders are easily formed by a wide range of molecules [7,32].…”

Section: Liquid Crystal Honeycombsmentioning

confidence: 99%

“…The resulting honeycomb cells of polygonal cross section and infinite length are filled by the fluid lateral chains. Depending on the ratio of the volume of the chains to the length of the rod-like core, cells ranging from triangular [41] via rhombic, square and pentagonal to hexagonal were obtained [32]. Projected on a Euclidian plane, most observed honeycombs are Archimedean tilings [42] by polygons, i.e.…”

Section: Liquid Crystal Honeycombsmentioning

confidence: 99%

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Complex tiling patterns in liquid crystals

et al. 2011

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In this account recent progress in enhancing the complexity of liquid crystal self-assembly is highlighted. The discussed superstructures are formed mainly by polyphilic T-shaped and X-shaped molecules composed of a rod-like core, tethered with glycerol units at both ends and flexible non-polar chain(s) in lateral position, but also related inverted molecular structures are considered. A series of honeycomb phases composed of polygonal cylinders ranging from triangular to hexagonal, followed by giant cylinder honeycombs is observed for ternary T-shaped polyphiles on increasing the size of the lateral chain(s). Increasing the chain size further leads to new modes of lamellar organization followed by three-dimensional and two-dimensional structures incorporating branched and non-branched axial rod-bundles. Grafting incompatible chains to opposite sides of the rod-like core leads to quaternary X-shaped polyphiles. These form liquid crystalline honeycombs where different cells are filled with different material. Projected on an Euclidian plane, all honeycomb phases can be described either by uniformly coloured Archimedean and Laves tiling patterns (T-shaped polyphiles) or as multi-colour tiling patterns (X-shaped polyphiles). It is shown that geometric frustration, combined with the tendency to segregate incompatible chains into different compartments and the need to find a periodic tiling pattern, leads to a significant increase in the complexity of soft self-assembly. Mixing of different chains greatly enhances the number of possible 'colours' and in this way, periodic structures comprising up to seven distinct compartments can be generated. Relations to biological self-assembly are discussed shortly.

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Section: X-shaped Polyphiles and Multi-colour Tilingsmentioning

confidence: 99%

Section: X-shaped Polyphiles and Multi-colour Tilingsmentioning

confidence: 99%

Section: Liquid Crystal Honeycombsmentioning

confidence: 99%

Section: Liquid Crystal Honeycombsmentioning

confidence: 99%

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Complex tiling patterns in liquid crystals

et al. 2011

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“…Herein we focus on X-shaped bolapolyphiles involving a relatively long oligo(phenylene ethynylene) (OPE) core (Scheme 2) [23,[43][44][45][46][47]. For these compounds with long rigid cores, the prismatic cell size of the honeycombs is limited to triangular [48,49] and square shapes [50], even if very long and bulky lateral chains are used. These large molecules with molecular weights between 1 and 2 kg·mol −1 could be considered as triblock rod-coil oligomers with strictly uniform size distribution [16,51].…”

Section: Methodsmentioning

confidence: 99%

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

Poppe

Ebert

et al. 2017

Polymers

Self Cite

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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.

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Soft Rectangular Sub‐5 nm Tiling Patterns by Liquid Crystalline Self‐Assembly of T‐Shaped Bolapolyphiles

Lehmann

Scholte

Prehm

et al. 2018

Adv Funct Materials

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Square and other rectangular nanoscale tiling patterns are of contemporary interest for soft lithography. Though soft square patterns on a ≈40 nm length scale can be achieved with block copolymers, even smaller tiling patterns below 5 nm can be expected for liquid crystalline phases of small molecules. However, these usually form lamellar and hexagonal morphologies and thus the challenge is to specifically design liquid crystal (LC) phases forming square and rectangular structures, being compatible with industrial standards. Here, two distinct types of liquid crystalline rectangular tiling patterns are reported occurring in a series of T-shaped p-terphenyl-based bolapolyphiles. By directed side chain engineering sub-5 nm sized quadrangular honeycombs with rhombic (c2mm), square (p4mm), and rectangular (p2mm) shapes of the cells are formed by spontaneous self-assembly. The rectangular honeycomb with p2mm lattice represents a new mode of LC self-assembly in polygonal honeycombs. In addition, pentagonal and hexagonal tiling motifs can be obtained by molecular fine tuning.

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Liquid‐Crystalline Triangle Honeycomb Formed by a Dithiophene‐Based X‐Shaped Bolaamphiphile

Cited by 14 publications

References 26 publications

Complex tiling patterns in liquid crystals

Complex tiling patterns in liquid crystals

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

Soft Rectangular Sub‐5 nm Tiling Patterns by Liquid Crystalline Self‐Assembly of T‐Shaped Bolapolyphiles

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