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

Reppe, Tino; Poppe, Silvio; Cai, Xiaoqian; Cao, Yu; Liu, Feng; Tschierske, Carsten

doi:10.1039/d0sc01396j

Cited by 23 publications

(66 citation statements)

References 58 publications

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“…Compound 1/6 [44] was shown in previous work to form a uniques equence of three mirror symmetry broken phases with conglomerate texture (Figure 8a). At the transition from the ordinary isotropic liquid (Iso) on cooling ap ercolated Iso 1 phase is formed around1 30 8C.…”

Section: Non-symmetric Tetracatenars With Additional Fluorine Substitmentioning

confidence: 76%

“…1/0 [44] HHHH: Cr 126 [52.2] Iso;C:Iso 110 [ 27.3] Cr --1/1 [44] OMe HHH: Cr 127 [36.3] Iso;C:Iso 115 [ 36.4] Cr --1/2 [44] OEt 12.9 (6.9) 1/14 [44] OC 14 [29a] for DSCs, see All compounds 2/X with polar substituents form exclusively the achiral Ia3 d phase and no I23 [ * ] or Iso 1 [ * ] phase can be observed, whereas compounds with alkyloxy chains, acting as donor-substituents (s m + s p = À0.22 for OC 4 H 9 ) [51] form as equence Ia3 d (L) -I23 [ * ] -Ia3 d (S) upon chain elongation. [9b,44,45, 53] The number of molecules in the cross-section of the networks (n raft , see Tables 3a nd S5) is 3.5-3.8 for the fluorinated compounds and 4.5-4.6 for the NO 2 and CN substituted compounds.…”

Section: Tricatenar Compoundswith Polar Substituents At the Apexmentioning

confidence: 99%

“…This is achiral and becomes chiral at the next phase transition at 123 8Cw hich is attributed to at ransition to an Iso 1 (Figure 8a andT able 4). [44] Fluorination in the peripheral3positiona tt he less substituted end (compound 3/ 3 F6)r etains the fundamental phase sequence, though the Iso 1…”

Section: Non-symmetric Tetracatenars With Additional Fluorine Substitmentioning

confidence: 99%

“…[45,47] These Iso 1 [ * ] phases usually occur besides one of the Cub bi phases and therefore they are considered as liquid network phases. [38,44] The 4,4'-diphenylbenzil derived polycatenars 1/n (Scheme2) with at orsion of the O = CÀC=Ob ond, [48] represent transiently chiral molecules, [38] whichw ere recentlys hown to even form a sequence of three mirror symmetry broken mesophases, thus transferring chirality from the isotropic liquid (Iso 1…”

Section: Introductionmentioning

confidence: 99%

“…[ * ] )v ia the liquid crystalline( Cub bi /I23 [ * ] )t ot he crystallines tate (Cr Iso [ * ] ). [44] Herein we expand this class of compounds by investigating the importance of the core length (compounds 4/n and 5 in Scheme2)a nd the effect of polar substituents in lateralp osition (compounds 3/Yn)ora to ne end (at the apex, compounds 2/X in Scheme 2) on the self-assembly,n etwork formation and spontaneous mirror symmetry breaking in the liquid state.…”

Section: Introductionmentioning

confidence: 99%

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

Reppe

Poppe

Tschierske

2020

Chemistry A European J

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Spontaneousd evelopment of chirality in systems composed of achiral molecules is important for new routes to asymmetricsynthesis, chiral superstructures and materials, as well as for the understanding of the mechanisms of emergence of prebiotic chirality.H erein, it is shown that the 4,4'diphenylbenzil unit is au niversal transiently chiral bent building block for the design of multi-chained (polycatenar) rod-like molecules capable of forming aw idev ariety of helically twisted network structures in the liquid,t he 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 Ia3 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 am irror symmetry broken liquid.R eplacing Fb yC lo rB rf urtheri ncreasest he twist,l eading to as hort pitch doubleg yroid Ia3 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.

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Section: Non-symmetric Tetracatenars With Additional Fluorine Substitmentioning

confidence: 76%

Section: Tricatenar Compoundswith Polar Substituents At the Apexmentioning

confidence: 99%

Section: Non-symmetric Tetracatenars With Additional Fluorine Substitmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

Reppe

Poppe

Tschierske

2020

Chemistry A European J

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Helical Networks of π‐Conjugated Rods – A Robust Design Concept for Bicontinuous Cubic Liquid Crystalline Phases with Achiral Ia3¯d and Chiral I23 Lattice

Dressel

Reppe

Poppe

et al. 2020

Adv Funct Materials

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Bicontinuous cubic liquid crystalline phases of π-conjugated molecules, representing self-assembled 3D-ordered interpenetrating networks with cubic symmetry, are receiving increasing attention due to their capacity for charge transport in all three dimensions and their inherent spontaneous helicity. Herein, a robust general design concept for creating bicontinuous cubic phases is reported. It is based on a nonsymmetric-substituted π-conjugated 5,5′-diphenyl-2,2′-bithiophene platform with one end containing three outfanning flexible chains and with a range of substituents at the other end (the apex). The cubic phases are stable over broad temperature ranges, often down to ambient temperature, and tolerate a wide range of apex substitution patterns, allowing structural diversity and tailoring of the cubic phase type and application-relevant properties. With an increasing number and size of apex substituents, a sequence of three different modes of cubic self-assembly is observed, following an increasing helical twist. Thus, two ranges of the achiral double network Ia3d phase range can be distinguished, a long pitch and a short pitch, with the chiral triple network I23 cubic phase in the intermediate pitch range. The findings provide a new prospect for the directed design of cubic phase-forming functional materials based on spontaneously formed helical network liquid crystals with tunable application specific properties.

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Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT‐Derived Polycatenar Molecules

Kwon

Cai

et al. 2021

Adv Funct Materials

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First examples of multichain (polycatenar) compounds, based on the π‐conjugated [1]benzothieno[3,2‐b]benzothiophene unit are designed, synthesized, and their soft self‐assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan‐shaped 2‐brominated 3,4,5‐trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non‐dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.

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

Abstract: Achiral multi-chain benzil derivatives provide a missing link between mirror symmetry breaking phenomena in fluid systems of polycatenar and bent-core liquid crystals.

Cited by 23 publications

References 58 publications

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

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

Helical Networks of π‐Conjugated Rods – A Robust Design Concept for Bicontinuous Cubic Liquid Crystalline Phases with Achiral Ia3¯d and Chiral I23 Lattice

Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT‐Derived Polycatenar Molecules

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