Cholesterol-based nonsymmetric dimers comprising phenyl 4-(benzoyloxy)benzoate core: the occurrence of frustrated phases

The synthesis and mesomorphism of sixteen new nonsymmetric liquid crystal dimers formed by covalently attaching cholesterol with a three-ring mesogenic core, namely, phenyl 4-(benzoyloxy)benzoate, via an omega-oxyalkanoyl spacer are described. The lengths of the terminal chain attached to the three-ring core, as well as those of the omega-oxyalkanoyl spacer, have been varied; accordingly, they have been grouped into four sets. They display an enantiotropic chiral nematic (N*) behaviour with the isotropization temperature crossing over 200 C-o. Four dimers having an odd-parity spacer were found to additionally show blue phase-I/II (BP-I/II), and the smectic A (SmA) phase. Twelve dimers with an even-membered spacer also stabilise either chiral smectic C (SmC*) or twist grain boundary (TGB) phase having SmC* slabs (TGBC* phase). The dimers with longer spacer and terminal tail favour the formation of the TGBC* phase. Thus, the lengths of both the terminal tail and the central spacer are seen to direct the type of mesophase and liquid crystal phase sequences to be formed. X-ray diffraction measurements have been carried out on representative samples to corroborate the structure of the mesophases. The N* phase has been probed with the aid of CD technique to figure out the handedness of the helicoidal structure.