Twist-bend nematogenic supramolecular dimers and trimers formed by hydrogen bonding

A selection of novel non-symmetric supramolecular liquid crystal dimers and trimers formed by hydrogen-bonding have been prepared and their phase behaviour characterised by polarised optical microscopy, X-ray diffraction and temperature-dependent Fourier-transform infrared spectroscopy. We mix the bent twist-bend nematogen 4-[6-(4’-cyanobiphenyl-4-yl) hexyloxy]-benzoic acid (CB6OBA) with a series of small stilbazole-based compounds 4-[(E)-2-(n-alkoxyphenyl)ethenyl]pyridines (nOS) of varying terminal chain length (n) to obtain the CB6OBA:nOS complexes. Complexes with n ≤ 7 exhibit nematic and twist-bend nematic behaviour, followed on cooling by a smectic C phase for n = 4–7, and finally, a hexatic-type smectic X phase for n = 3–7. Mixtures with n = 8–10 exhibit a smectic A phase below the conventional nematic phase, and on further cooling, a biaxial smectic Ab phase and the same hexatic-type SmX phase. Supramolecular trimers, CB6OBA:CB6OS and CB6OBA:1OB6OS, formed between CB6OBA and dimeric stilbazoles [(E)-2-(4-{[6-(4’-methoxy[1,1’-biphenyl]-4-yl)hexyl]oxy}phenyl)ethenyl]pyridine (1OB6OS) or 4-[(E)-4’-(6-{4-[(E)-2-(pyridin-4-yl)ethenyl]phenoxy}hexyl)[1,1’-biphenyl]-4-carbonitrile (CB6OS), exhibit nematic and twist-bend nematic phases, and are the first hydrogen-bonded trimers consisting of unlike donor and acceptor fragments to do so.