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In searching for new functional self-assembling materials a multicomponent ferroelectric liquid crystalline mixtures with features appropriate for utilization in photonic and electro-optic devices have been designed. Designed mixtures are composed of bicyclic pyrimidine achiral compounds and chiral dopants with an oligophenyl rigid core and two homochiral terminal chains. Basic mesomorphic, electro-optical and structural properties have been carefully studied and discussed. For several mixtures stable enantiotropic ferroelectric phase with very good alignment and desired functional features in surface stabilized geometry have been found. Based on these properties and computational as well as conformational analysis of chiral dopants, the structure-property relations have been established and analysed. Unlabelled Image • Mixtures of olighophenyl chiral dopants and achiral mixture have been designed. • The structure–property correlations for designed mixtures have been established. • Desired tilt angle, low viscosity and spontaneous polarization are observed. • Good electro-optical performance of SSFLC structure are achieved. • The designed mixtures can be used for functional optoelectronic and photonic devices. [ABSTRACT FROM AUTHOR]