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A small series of dendrimers consisting of a star-shaped triphenylbenzene core unit and bulky lateral groups was synthesised and their mesomorphic properties were investigated via differential scanning calorimetry, polarising optical microscopy and small- and wide-angle X-ray scattering (WAXS). The dendrimers showed two enantiotropic hexagonal columnar mesophases. The combination of temperature-dependent and fibre-extruded WAXS revealed a helical arrangement in the low-temperature and a zig-zag orientation in the high-temperature mesophase. Furthermore, at the mesophase-to-mesophase transition, the intracolumnar reorganisation and the intercolumnar lattice extension occurred at different time scales, with the latter process being the slower one. [ABSTRACT FROM AUTHOR]

A series of MIDA (N-methylimino diacetic acid) boronates carrying 4-alkoxy, 3,4-bisalkoxy, or 3,4,5-trisalkoxyphenyl substituents were synthesized and their mesomorphic properties characterized by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction (XRD) techniques such as small- and wide-angle X-ray scattering (SAXS and WAXS, respectively). Most derivatives were liquid crystalline. In the case of mono- and bisalkoxy-substituted derivatives, C 6 chains already induced smectic A (SmA) mesophases despite the bulky MIDA head group. With increasing chain length, columnar hexagonal (Col h ) phases replaced SmA phases in the disubstituted series. Quantum chemical calculations on a series of MIDA boronates show that the B-N bond is a dative bond with a positive charge on the boron atom and negative charges on the nitrogen and oxygen atoms. In addition, no π-interaction between the aryl moiety and B-N bond was found, thus the mesogenic unit is electronically decoupled from the MIDA head group. These theoretical findings were supported by IR and Raman spectra as well as by asingle crystal structure analysis of 4-ethoxyphenyl MIDA boronate. Calculations of the electrostatic potential of the MIDA boronate reveal a special polarity pattern that can support the formation of a two-dimensional network and is likely to explain the liquid crystalline self-assembly. The absence of any electronic cross-talk between the MIDA head group and B-aryl or B-alkyl substituents allows the efficient tailoring of the mesophase type through variation of the substituents., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Synthetic strategies were developed to prepare l-tyrosine-based ionic liquid crystals with structural variations at the carboxylic and phenolic OH groups as well as the amino functionality. Salt metathesis additionally led to counterion variation. The liquid-crystalline properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (WAXS, SAXS). The symmetrical ILC chlorides bearing the same alkyl chain at both the ester and ether but either an acyclic or cyclic guanidinium group displayed enantiotropic SmA 2 mesophases with phase widths of 31-88 K irrespective of the head group. It was particularly the replacement of chloride in the acyclic guanidinium ILC by hexafluorophosphate that induced a phase change from SmA 2 to Col r . This phase change was attributed to a higher curvature of the interface due to the larger anion, which increased the effective head group cross-sectional area of the amphiphilic ILC. The unsymmetrical acyclic guanidinium chlorides, bearing a constant C 14 ester and variable alkyl chains on the phenolic position, formed enantiotropic SmA 2 phases. The derivative with the largest difference in chain lengths, however, displayed a Col r phase, resulting from discoid aggregates of the cone-shaped guanidinium chloride. The results are discussed in terms of the packing parameters, which indicate that the phase behaviour of the thermotropic tyrosine-based ILCs shows analogies to those of lyotropic liquid crystals., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)