According to our present knowledge, the spontaneous resolution of racemic mixtures of chiral molecules or chiral conformers of achiral molecules into macroscopic chiral superstructures requires the confinement of these molecules in a crystal lattice, on surfaces or in other well-ordered assemblies. Herein we provide the first experimental evidence that mirror-symmetry breaking can also take place at a liquid-liquid phase transition in isotropic liquids of achiral molecules, even at relatively high temperatures around 200 °C. It is proposed that cooperative segregation of enantiomorphic molecular conformations gives rise to a conglomerate of two chiral and immiscible liquids. In these liquid conglomerates a strong chiral amplification was observed, which led to degeneracy from a stochastic distribution and eventually provided uniform chirality. We anticipate that this work will contribute to the understanding of symmetry breaking in soft matter and provide a new tool for the identification of chirality traces, and possibly affect the discussion of the emergence of chirality in prebiotic systems.

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

Achiral compounds with an alicyclic apex form a chiral cubic phase either for a specific ring-size or by mixing of small- and large-ring compounds.

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.

In article number 2004353, Goran Ungar, Carsten Tschierske, and co‐workers present a general design concept of bicontinuous cubic liquid crystals consisting of helical networks that are stable over a broad temperature range. Increasingly bulky substituents cause increasing helical twist between the three‐chain 2,2′‐bithiophene based molecular rods, resulting in a sequence of three distinct phases: two ranges of achiral double network (Iatrue3¯d) separated by a range of spontaneously chiral triple network (I23).