LAUSR

ABSTRACT Azulenes and crystal-smectic E-phases (SmE) both have recently raised attention for the design of novel organic devices. However, the combination of self-assembly into soft-crystalline mesophases with the unique electronic properties of azulene derivatives has not been probed yet. Therefore, a convenient synthesis of 6-alkoxy-2-bromoazulenes, forming ambient temperature SmE-phases, was developed. Differential scanning calorimetry, polarising optical microscopy and X-ray diffraction provided insight into the self-assembly of the liquid crystalline phase. Comparison of experimental data and quantum chemical calculations of 6-alkoxy-2-bromoazulene with the ‘inverted’ 2-alkoxy-6-bromoazulene revealed large differences in polarity, which affected optical and mesomorphic properties, and provided insight into structure–property relationships enabling the design of novel thin-film devices.