The diversity of phase morphologies observed recently in star‐branched liquid‐crystalline and polymeric compounds containing at least three immiscible segments is reviewed. Bolaamphiphiles and facial amphiphiles with rodlike aromatic cores, two end‐groups, and one (T‐shape) or two (X‐shape) chains attached laterally to the core, form numerous honeycomblike liquid‐crystal phases, as well as a variety of novel lamellar and 3D‐ordered mesophases. Molecular self‐organization is described in bulk phases and in thin films on solid and liquid surfaces, as well as in Langmuir–Blodgett films. The remarkably reversible formation of mono‐ and trilayer films is highlighted. In the bulk, T‐shaped “rod–coil” molecules without appended end‐groups form predominantly lamellar phases if the core is a straight rod, but the bent‐core variety forms hexagonal honeycombs. Furthermore, self‐assembly of “Janus”‐type molecules, is discussed. Also covered is the diversity of morphologies observed in miktoarm star terpolymers, i.e., polymers with three different and incompatible arms of well defined lengths. Similarities and differences are highlighted between the liquid‐crystal morphologies on the 3–15 nm scale and the polymer morphologies on the scale of 10–100 nm. A separate section is dedicated to computer simulations of such systems, particularly those using dissipative particle and molecular dynamics. Of special interest are the recently synthesised X‐shaped tetraphilic molecules, where two different and incompatible side‐chains are attached at opposite sides of the rodlike core. The tendency for their phase separation produces liquid‐crystal honeycombs with cells of different compositions that can be represented as a plane paved with different colored tiles. The independent variation of chain length and “color” creates the potential for developing a considerable range of complex new 2D and 3D soft nanostructures. Analogous X‐shaped rod–coil compounds with unequal side groups are also of considerable interest, forming tubular lyotropic structures capable of confining strings of guest molecules.

Aggregation in Langmuir films is usually understood as being a disorderly grouping of molecules turning into chaotic three‐dimensional aggregates and is considered an unwanted phenomenon causing irreversible changes. In this work we present the studies of 11 compounds from the group of specific surfactants, known as bolaamphiphiles, that exhibit reversible aggregation and, in many cases, transition to well‐defined multilayers, which can be considered as a layering transition. These bolaamphiphiles incorporate rigid π‐conjugated aromatics as hydrophobic cores, glycerol‐based polar groups and hydrophobic lateral chains. Molecules of different shapes (X‐, T‐, and anchor) were studied and compared. The key property of these compounds is the partial fluorination of the lateral chains linked to the rigid cores of the molecules. The most interesting feature of the compounds is that, depending on their shape and degree of fluorination, they are able to resist aggregation and preserve a monolayer structure up to relatively high surface pressures (T‐shaped and some X‐shaped molecules), or create well‐defined trilayers (X‐ and anchor‐shaped molecules). Experimental studies were performed using Langmuir balance, surface potential and X‐ray reflectivity measurements.

N‐Centred benzene‐1,3,5‐tricarboxamides (N‐BTAs) composed of chiral and achiral alkyl substituents were synthesised and their solid‐state behaviour and self‐assembly in dilute alkane solutions were investigated. A combination of differential scanning calorimetry (DSC), polarisation optical microscopy (POM) and X‐ray diffraction revealed that the chiral N‐BTA derivatives with branched 3,7‐dimethyloctanoyl chains were liquid crystalline and the mesophase was assigned as Col_ho. In contrast, N‐BTA derivatives with linear tetradecanoyl or octanoyl chains lacked a mesophase and were obtained as crystalline compounds. Variable‐temperature infrared spectroscopy showed the presence of threefold, intermolecular hydrogen bonding between neighbouring molecules in the mesophase of the chiral N‐BTAs. In the crystalline state at room temperature a more complicated packing between the molecules was observed. Ultraviolet and circular dichroism spectroscopy on dilute solutions of N‐BTAs revealed a cooperative self‐assembly behaviour of the N‐BTA molecules into supramolecular polymers with preferred helicity when chiral alkyl chains were present. Both the sergeants‐and‐soldiers as well as the majority‐rules principles were operative in stacks of N‐BTAs. In fact, the self‐assembly of N‐BTAs resembles closely that of their carbonyl (CO)‐centred counterparts, with the exception that aggregation is weaker and amplification of chirality is less pronounced. The differences in the self‐assembly of N‐ and CO‐BTAs were analysed by density functional theory (DFT) calculations. These reveal a substantially lower interaction energy between the monomeric units in the supramolecular polymers of N‐BTAs. The lower interaction energy is due to the higher energy penalty for rotation around the PhNH bond compared to the PhCO bond and the diminished magnitude of dipole–dipole interactions. Finally, we observed that mixed stacks are formed in dilute solution when mixing N‐BTAs and CO BTAs.