Zeolite-like liquid crystals

Poppe, Silvio; Lehmann, Anne; Scholte, Alexander; Prehm, Marko; Zeng, Xiangbing; Ungar, Goran; Tschierske, Carsten

doi:10.1038/ncomms9637

Cited by 33 publications

(23 citation statements)

References 35 publications

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“…Ia " 3d = DG cubic phase with Ia " 3d symmetry; p2 = honeycomb LC phase with p2lattice; [22] Lam Sm = lamellar phase with coplanar bundles and periodicity in the layers; [23] Iso = isotropic liquid;for DSCs, see Figure S1; for XRD data, see Tables S1 and S2. Figure S4d).…”

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confidence: 99%

A Self‐Assembled Bicontinuous Cubic Phase with a Single‐Diamond Network

et al. 2019

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The first single-diamond cubic phase in al iquid crystal is reported. This skeletal structure with the Fd " 3mspace group is formed by self-assembly of bolaamphiphiles with swallow-tailed lateral chains.I tc onsists of bundles of pconjugated p-terphenyl rods fused into an infinite network by hydrogen-bonded spheres at tetrahedral four-way junctions. We also present aq uantitative model relating molecular architecture to the space-filling requirements of six possible bicontinuous cubic phases,t hat is,t he single-and doublenetwork versions of gyroid, diamond, and "plumber'sn ightmare".Among the most intriguing self-assembled nano-and mesoscale soft-matter structures are the cubic phases formed by lyotropic and thermotropic liquid crystals (LCs), by block copolymers, [1,2] and by nanoparticle arrays. [3][4][5] Tw o classes of cubic phases can be distinguished, the "bicontinuous" and the "micellar" types. [6,7] Them icellar phases represent periodic arrays of spheres on ac ubic lattice, whereas the bicontinuous phases are more complex and usually formed by two networks divided by aminimal surface with aconstant mean curvature.Depending on the symmetry, the double gyroid (DG, Ia " 3d,Q 230 ), the double diamond (DD; Pn " 3m,Q 224 ), and the body-centered plumber'sn ightmare ("double primitive") cubic phases (DP; Im3 m,Q 229 )w ith junction valencies of n = 3, 4, and 6, respectively,c an be distinguished (Figure 1a-c). Figure 6. Models showing a) the micellar Fd " 3m cubic phase [27,28] and b) the new SD bicontinuous cubic phase of compounds 1/18-11/22.

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confidence: 99%

A Self‐Assembled Bicontinuous Cubic Phase with a Single‐Diamond Network

et al. 2019

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“…As observed experimentally [10][11][12][13][14][15][16][17] and supported by simulations [18][19][20][21], there is a transition from rhombic or triangular via square, pentagonal to hexagonal cells with growing lateral chain volume or with decreasing rigid core length. Occasionally, complex tiling patterns composed of cells with different shapes were found [22], especially if different lateral chains (e.g., fluorinated and non-fluorinated) were combined [23][24][25]. For lateral groups with Bolaamphiphiles are also capable of forming supramolecular polymers and networks by terminal (end-to-end) aggregation (Scheme 1c,d) [3][4][5][6].…”

Section: Methodsmentioning

confidence: 99%

“…As observed experimentally [10][11][12][13][14][15][16][17] and supported by simulations [18][19][20][21], there is a transition from rhombic or triangular via square, pentagonal to hexagonal cells with growing lateral chain volume or with decreasing rigid core length. Occasionally, complex tiling patterns composed of cells with different shapes were found [22], especially if different lateral chains (e.g., fluorinated and further increased volume, giant honeycombs (Figure 1i-k) [25][26][27] and lamellar phases with coplanar organization of rods (Lam) (Figure 1l-n) were observed [28][29][30][31]. For compounds with branched lateral chains, coaxial rod-bundle phases with cubic network structure (Figure 1o) [32,33] or forming columns on a hexagonal lattice were reported (Figure 1p) [34,35].…”

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

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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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“…Herein we present a new series of T‐shaped polyphilic compounds 2/ n , based on the p ‐terphenyl core and having a single normal alkyl lateral chain C n H 2 n +1 grafted to the middle benzene ring (see Table 1 ). In the 2/ n series the chain length was varied from n = 5 to 22.…”

Section: Introductionmentioning

confidence: 99%

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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Zeolite-like liquid crystals

Cited by 33 publications

References 35 publications

A Self‐Assembled Bicontinuous Cubic Phase with a Single‐Diamond Network

A Self‐Assembled Bicontinuous Cubic Phase with a Single‐Diamond Network

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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