Photoswitching of Ferroelectric Liquid Crystals Using Unsymmetrical Chiral Thioindigo Dopants: Photoinduced Inversion of the Sign of Spontaneous Polarization

Abstract A new unsymmetrical chiral thioindigo dopant 6‐[(R,R)‐2,3‐difluorooct‐1‐yloxy]‐5′‐nitro‐6′‐[(R)‐2‐octyloxy]thioindigo (4) designed to photoinvert the sign of spontaneous polarization (P_S) in a ferroelectric chiral smectic C (SmC*) liquid crystal was prepared using a synthetic approach previously developed in our laboratory. In this new “ambidextrous” design, the (R)‐2‐octyloxy side‐chain is sterically coupled to the thioindigo core and induces a positive P_S, whereas the (R,R)‐2,3‐difluorooctyloxy side‐chain is decoupled from the core and induces a larger negative P_S. In the trans form, this dopant induces a negative polarization in the SmC host (+)‐4‐(4‐methylhexyloxy)phenyl 4‐decyloxybenzoate (PhB). Irradiation of a 1 mol‐% mixture of 4 in PhB at λ = 510 nm caused a sign inversion of P_S, from –0.88 to +0.42 nC cm^–2 at T – T_C = –5 °C, which is consistent with an increase in the polarization power of the coupled 2‐octyloxy/thioindigo unit over that of the 2,3‐difluorooctyloxy unit, due to the increase in transverse dipole moment of the thioindigo core upon trans–cis photoisomerization. The P_S sign inversion was confirmed by a surface‐stabilized ferroelectric liquid crystal photoswitching experiment. Spectroscopic measurements on films of the doped liquid crystal mixtures showed that trans–cis photoisomerization is gradually suppressed with increasing dopant mole fraction, possibly as a result of increased dopant aggregation.