Competing ferroelectric and smectic order: modulated structures through molecular design

Abstract

We demonstrate that the balance between polar and positional order can be systematically tuned through molecular engineering, providing direct control over the emergence of polar and modulated liquid-crystalline phases, allowing for versatile strategy for the design of functional ferroelectric soft materials. We show that polar orthogonal smectic phases (SmAF and SmAAF), promoted by the self-segregation of aromatic cores and sufficiently long terminal chains, are readily destabilized by strong longitudinal dipolar interactions that energetically penalize parallel alignment of molecular dipoles within a smectic layer. In contrast, the tilted ferroelectric SmCF phase is remarkably robust across the entire homologous series, indicating that molecular tilt efficiently relieves dipolar frustration within the smectic layers. We further demonstrate that the interplay between microsegregation and electrostatic interactions stabilizes the new modulated SmCM phase, characterized by incommensurate electron-density waves, particularly for compounds with short terminal chains. For longer homologs controlling the spatial distribution of fluorinated molecular fragments and terminal-chain length enabled the targeted formation of broken-layer-type modulated polar phases (2D or 3D).