Thermotropic ionic liquid crystals based on the flavylium scaffold have been synthesized and studied for their structure‐properties relationship for the first time. The mesogens were probed by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X‐ray diffraction (XRD). Low numbers of alkoxy side chains resulted in smectic (SmA) and lamello‐columnar (LamCol) phases, whereas higher substituted flavylium salts showed Colro as well as ordered and disordered columnar (Colho, Colhd) mesophases. Mesophase width ranged from 13 K to 220 K, giving access to room temperature liquid crystals. The optical properties of the synthesized compounds were probed towards absorption and emission properties. Strong absorption with maxima between 444 and 507 nm was observed, and some chromophores were highly emissive with quantum yields up to 99 %. Ultimately, mesogenic and dye properties were examined by temperature‐dependent emissive experiments in the solid state.

Crown ethers and their derivatives are versatile building blocks for the design of supramolecular materials. They can be functionalized at will and are well known for their abilities to complex with alkali cations. Here, we show that emissive lanthanide free hybrid materials can be generated by using such building blocks. The organic tribenzo[18]crown-6 central core was functionalized via six-fold Suzuki cross-coupling as a key reaction with three o-terphenyl units which could be converted into their corresponding triphenylenes by the Scholl reaction, leading to novel liquid-crystalline columnar materials. Selected tribenzo[18]crown-6 o-terphenyls could interact with emissive ternary metal cluster compound salts to generate hybrid materials combining the properties of both moieties. Due to synergistic effects and despite the anisometry of the cluster compounds, individual properties such as liquid-crystalline phase stability of the organic part and emission abilities of its inorganic counter-part are enhanced in the hybrid compounds.

A series of tetraguanidinium tetraphenylethene (TPE) arylsulfonates with different chain lengths was prepared via ionic self-assembly of tetraguanidinium TPE chloride and the respective methyl arylsulfonates. Liquid crystalline properties were studied by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. Tetraguanidinium TPE arylsulfonates with chain lengths of C8 -C12 displayed hexagonal columnar mesophases over a broad temperature range, while derivatives with longer chains showed oblique columnar phases. In solution all compounds displayed aggregation-induced emission behaviour. Temperature-dependent luminescence spectra of the bulk phase of the tetraguanidinium TPE arylsulfonate with C14 side chains revealed a strong luminescence both in the solid state and the oblique columnar mesophase. The emission behaviour was rationalized by a unique combination of restriction of intramolecular rotation of the TPE core, Coulomb interaction between the guanidinium cations and − interactions of the anionic arylsulfonate moieties.

Aminocyclopropenium ions have raised much attention as organocatalysts and redox active polymers. However, the self‐assembly of amphiphilic aminocyclopropenium ions remains challenging. The first deltic ionic liquid crystals based on aminocyclopropenium ions have been developed. Differential scanning calorimetry, polarizing optical microscopy and X‐ray diffraction provided insight into the unique self‐assembly and nanosegregation of these liquid crystals. While the combination of small headgroups with linear p‐alkoxyphenyl units led to bilayer‐type smectic mesophases, wedge‐shaped units resulted in columnar mesophases. Upon increasing the size and polyphilicity of the aminocyclopropenium headgroup, a lamellar phase was formed.

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ILCs consisting of cationic head group–spacer–fluorenone central core–side chain show de Vries-like behaviour.

To probe the influence of electrostatic interactions on the mesomorphic self-assembly and phase behaviour of hybrid liquid crystals a series of crown ether/tyrosine hybrid systems was prepared by Steglich esterification of alkyl N-(tert-butoxycarbonyl)-l-tyrosinates with 4-carboxybenzo[15]crown-5 and 4-carboxybenzo[18]crown-6. The obtained derivatives allowed further manipulations at the NH functional group and complexation of the crown ether unit with NaI to give neutral or charged hybrid materials. All compounds were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (XRD) measurements. Neither the variation of the N-protecting group, introduction of charge at the N-terminus nor anion exchange (Cl vs. I) resulted in mesomorphism. In contrast, N-Boc-protected and unprotected hybrids formed rectangular columnar (Col) mesophases with phase widths up to 35 K. NaI complexation switched these neutral thermotropic derivatives into ionic liquid crystals (ILCs) and induced a change of mesophase type from Col to smectic A (SmA). A comparison of experimentally obtained layer distances and theoretically calculated molecular lengths indicated bilayer SmA formation with interdigitated alkyl chains. Packing models for both mesophase types are proposed and discussed with respect to stabilizing interactions.

Tailoring of phase transition temperatures of columnar liquid crystals by side chain variation is often associated with an undesired change in the mesophase type and/or geometry. To overcome this problem phenoxy-terminated side chains rather than alkyl side chains were grafted onto triphenylbenzenes, which resulted in reduced clearing points, while melting points were little affected. More importantly, helical columnar self-assembly was not compromised.