Thioether-Linked Liquid Crystal Trimers: Odd–Even Effects of Spacers and the Influence of Thioether Bonds on Phase Behavior

We report the synthesis, phase-transition behavior, and mesophase structures of the first homologous series of thioether-linked liquid crystal (LC) trimers, 4,4′-bis[ω-(4-cyanobiphenyl-4′-ylthio)alkoxy]biphenyls (CBSnOBOnSCB with a wide range of spacer carbon numbers, n = 3–11). All CBSnOBOnSCB homologs exhibited LC phases. Interestingly, even-n and odd-n homologs showed monotropic layered smectic A (SmA) and pseudo-layered twist-bend nematic (N(TB)) phases, respectively, below a nematic (N) phase. This alternate formation, which depends on spacer chain parity, is attributed to different average molecular shapes, which are associated with the relative orientations of the biphenyl moieties: linear and bent shapes for even-n and odd-n homologs, respectively. In addition, X-ray diffraction analysis indicated a strong cybotactic N phase tendency, with a triply intercalated structure. The phase-transition behavior and LC phase structures of thioether-linked CBSnOBOnSCB were compared with those of the all-ether-linked classic LC trimers CBOnOBOnOCB. Overall, thioether linkages endowed CBSnOBOnSCB with a monotropic LC tendency and lowered phase-transition temperatures, compared to those of CBOnOBOnOCB, for the same n. This is attributed to enhanced flexibility and bending (less molecular anisotropy) of the molecules, caused by the greater bond flexibility and smaller inner bond angles of the C–S–C bonds, compared to those of the C–O–C bonds.