Tailoring the dielectric and ferroelectric response of mixtures containing bent-core liquid crystals through light-irradiation and composition

[Display omitted] •Binary mixtures of bent-core liquid crystals show columnar and smectic phases with good miscibility.•All mixtures show mesomorphic behaviour, with reductions in their clearing points and liquid crystalline ranges.•The mixtures show strong dielectric response mainly promoted by the presence of ester groups in the bent-core molecules.•Reversible trans-to-cis photoisomerization of azobenzenes is applied to tune the molecular dipole moment, assessed by DFT.•Irradiation increases the conductivity of the equimolar mixture by two orders of magnitude. We report the mesomorphic behaviour, dielectric and ferroelectric properties, and computational modelling of binary mixtures containing two bent-core liquid crystals: the so-called NG75-COO (3,4́- Bis[4-(4-n-tetradecyloxybenzoyloxy)benzoyloxy]biphenyl), which forms smectic phases, and IP31- AzB (3,4′ - Bis[4-(4-n-tetradecyloxyphenylazo)benzoyloxy]biphenyl), which forms columnar phases. The phase diagram, assessed by polarised optical microscopy, shows that the binary mixtures retain the mesophase behaviour of the major component, whilst the equimolar mixture displays smectic-type phases. Dielectric and ferroelectric analyses were carried out on samples containing 10%, 50%, and 90% of IP31-AzB (molar %), and we also investigated structure–property correlations by differential functional theory. The NG75-COO/IP31-AzB mixtures undergo strong dielectric and ferroelectric response due to the presence of highly polarisable groups in the bent-core components, particularly at the ester groups. All the mixtures under study exhibit light-responsiveness induced by reversible E-to-Z photoisomerization (trans-to-cis) of the azobenzene group in IP31-AzB, together with an increase in the molecular dipole moment. The potential to tune the phase behaviour of the mixtures, as well as their dielectric and ferroelectric responses, are investigated by light irradiation under different conditions of intensity and temperature.