Observation of ferroelectric behaviour in non-symmetrical cholesterol-based bent-shaped dimers

Non-symmetrical cholesterol-based dimers have emerged as crucial materials in the field of liquid crystal research, owing to their remarkable ability to stabilize various exotic mesophases, including the blue phases (BPIII, BPII, BPI), cholesteric nematic (N*) phase, smectic blue phase (SmBP), twist grain boundary (TGB) phase, smectic A/smectic A* (SmA/SmA*) phase, and smectic C/smectic C* (SmC/SmC*) phase. These mesophases have garnered considerable attention due to their diverse applications in spatial light modulation, chiro-optical devices, optical switching, thermochromic materials, and more. In this study, we present the synthesis and comprehensive characterization of a series of non-symmetrical cholesterol-based bent-shaped dimers (1/12, 1/14, 1/16) in which the cholesterol unit is intricately linked to an aromatic mesogenic core through a flexible spacer. These novel materials exhibit the intriguing ability to stabilize a variety of mesophases, including the N*, TGBA, SmA, and SmC* phases. The chiro-optical properties of the helical SmC* phase have been meticulously investigated through temperature-dependent chiro-optical measurements, shedding light on their potential for advanced optoelectronic applications. Additionally, we have conducted a thorough examination of the physical characteristics of these cholesterol-based dimers, including static permittivity measurements, dielectric spectroscopy, and electro-optical performance analysis. Remarkably, two homologues (1/14, 1/16) exhibit negative dielectric anisotropy, a crucial parameter for liquid crystal devices. Furthermore, our investigation reveals that these materials exhibit ferroelectric behaviour in the SmC* phase, with compounds 1/14 and 1/16 demonstrating substantial spontaneous polarization (P_S) values of approximately 132 nC cm^-2 and 149 nC cm^-2, respectively. These findings underscore the potential of non-symmetrical cholesterol-based dimers as versatile components for the development of innovative electro-optical devices.