Journal of the American Chemical Society, Vol.118, No.40, 9557-9561, 1996
Induction of a Ferroelectric S-C-Asterisk Liquid-Crystal Phase by an Atropisomeric Dopant Derived from 4,4’-Dihydroxy-2,2’-Dimethyl-6,6’-Dinitrobiphenyl
We report the induction of a ferroelectric S-c* phase in two S-c liquid crystal hosts using a novel chiral dopant (-)-1 that incorporates an atropisomeric core derived from 4,4’-dihydroxy-2,2’-dimethyl-6,6’-dinitrobiphenyl. The racemic dopant was synthesized in 11 steps with an overall yield of 9% and resolved by chiral stationary phase HPLC in optically pure form. The magnitude and sign of the spontaneous polarization (P-s) induced by (-)-1 were found to depend strongly on the nature of the S-c host. In a cyclohexanecarbonitrile host, (-)-1 induces a positive polarization that is measurable over the dopant mole fraction range 0.02 < x(d) < 0.044; in a phenyl benzoate host, (-)-1 induces a negative polarization that falls below detection limit at x(d) less than or equal to 0.05. The polarization power (delta(p)) of (-)-1 in the cyclohexanecarbonitrile host is +170 nC/cm(2), which is more than eight times that estimated as upper limit in the phenyl benzoate host. These results are rationalized on the basis of the Boulder model for the molecular origins of P-s by modeling the conformational behavior of the biphenyl core in the achiral lattice of the S-c host using semiempirical AM1 calculations. The dependence of delta(p) on the nature of the S-c host is correlated to the large difference in negative dielectric anisotropy (epsilon parallel to - epsilon perpendicular to) of the two hosts.