New 4-bromoresorcinol based bent-core molecules with peripheral fluoro substituted azobenzene wings have been synthesized and the liquid crystalline self-assembly was investigated by differential scanning calorimetry (DSC), optical polarizing microscopy (POM), electro-optic studies and X-ray diffraction (XRD). A new type of optically isotropic mesophase composed of chiral domains with opposite handedness (dark conglomerate phases, DC phases) is observed, which for some homologues with medium alkyl chain length is stable down to ambient temperature. It is proposed that these DC phases are formed by helical twisted nano-domains of limited size and composed of the crystallized aromatic cores which are separated by the disordered alkyl chains. This structure is distinct from the previously known soft helical nano-filament phases (HNF phases, B4 phases) formed by extended crystalline nano-filaments and also distinct from the fluid sponge phases composed of deformed fluid layers. Comparison with related bent-core molecules having H, F, Cl, I, CH3 and CN groups in the 4-position at the resorcinol core, either with or without additional peripheral fluorines, provided information about the effects of these substituents on the tendency to form DC phases. Based on these relationships and by comparison with the minimum energy conformations obtained by DFT calculations a hypothesis is provided for the formation of DC phases depending on the molecular structure.

Stochastic achiral symmetry breaking in soft matter systems, leading to conglomerates of macroscopically chiral domains (so-called dark conglomerate ¼ DC phases) is of contemporary interest from a fundamental scientific point of view as well as for numerous potential applications in chirality sensing and noncentrosymmetric materials. Herein we report the synthesis and investigation of first azobenzene containing bent-core mesogens derived from 4-methylresorcinol forming DC phases with a new structure, distinct from the known fluid sponge-like distorted smectic phases as well as from the helical nano-filament phases (HNF phases, B 4 phases). The effects of chain length and other structural modifications on achiral symmetry breaking were investigated. Homologues with relatively short alkyl chains form achiral intercalated lamellar LC phases (B 6 phases), but on increasing the chains, these are replaced by the chiral and optically isotropic DC phases. Compounds with the longest alkyl chains form low birefringent crystalline conglomerates which represent less distorted versions of the optically isotropic DC-phases. Introducing additional peripheral substituents at both outer rings removes the DC phases. The DC phases were also removed and replaced by modulated smectic phases if the azo groups were replaced by ester units, showing that azo groups favour DC phase formation with new nanostructures, distinct from the previously known types.

A new series of azobenzene containing bent-core molecules incorporating 4-cyanoresorcinol as the central core unit exhibiting cybotactic nematic, rectangular, columnar, and different types of tilted smectic (SmC) phases are synthesized. The mesophase behavior and phase structures are characterized in bulk and freely suspended fi lms using a variety of experimental techniques. Depending on the chain length and temperature a series of different mesophases is observed in these compounds, ranging from cybotactic nematic via paraelectric SmC phases, polarization randomized SmC s P R phases to ferroelectric and antiferroelectric SmC phases, associated with increasing size and correlation length of the polar domains. Spontaneous formation of chiral domains is observed in the paraelectric SmC and the SmC s P R phases and discussed in relation with superstructural chirality, bend elastic constants, and surface effects.