Department of Chemistry, School of Natural and Computing Sciences, University of Aberdeen, Meston Building, Aberdeen, AB24 3UE, UK.
Liquid Crystal Institute and Chemical Physics Interdisciplinary Program, Kent State University, Kent, OH 44242, USA.
Soft Matter. 2016 Aug 10;12(32):6827-40. doi: 10.1039/c6sm00537c.
The synthesis and characterisation of the nonsymmetric liquid crystal dimer, 1-(4-cyanobiphenyl-4'-yloxy)-6-(4-cyanobiphenyl-4'-yl)hexane (CB6OCB) is reported. An enantiotropic nematic (N)-twist-bend nematic (NTB) phase transition is observed at 109 °C and a nematic-isotropic phase transition at 153 °C. The NTB phase assignment has been confirmed using polarised light microscopy, freeze fracture transmission electron microscopy (FFTEM), (2)H-NMR spectroscopy, and X-ray diffraction. The effective molecular length in both the NTB and N phases indicates a locally intercalated arrangement of the molecules, and the helicoidal pitch length in the NTB phase is estimated to be 8.9 nm. The surface anchoring properties of CB6OCB on a number of aligning layers is reported. A Landau model is applied to describe high-resolution heat capacity measurements in the vicinity of the NTB-N phase transition. Both the theory and heat capacity measurements agree with a very weak first-order phase transition. A complementary extended molecular field theory was found to be in suggestive accord with the (2)H-NMR studies of CB6OCB-d2, and those already known for CB7CB-d4. These include the reduced transition temperature, TNTBN/TNI, the order parameter of the mesogenic arms in the N phase close to the NTB-N transition, and the order parameter with respect to the helix axis which is related to the conical angle for the NTB phase.
报道了非对称液晶二聚体 1-(4-氰基联苯-4'-氧基)-6-(4-氰基联苯-4'-基)己烷 (CB6OCB) 的合成与表征。在 109°C 观察到各向异性向列(N)-扭曲向列(NTB)相转变,在 153°C 观察到向列-各向同性相转变。通过偏光显微镜、冷冻断裂透射电子显微镜 (FFTEM)、(2)H-NMR 光谱和 X 射线衍射证实了 NTB 相的归属。在 NTB 和 N 相中,有效分子长度表明分子局部层间排列,NTB 相中螺旋节距长度估计为 8.9nm。报道了 CB6OCB 在多种取向层上的表面锚定性质。应用朗道模型描述了 NTB-N 相转变附近的高分辨率热容测量。理论和热容测量都与非常弱的一级相变一致。补充的扩展分子场理论与 CB6OCB-d2 的(2)H-NMR 研究以及已经为 CB7CB-d4 所知的理论一致。这些包括降低的转变温度 TNTBN/TNI、接近 NTB-N 转变的 N 相中介晶臂的有序参数,以及与 NTB 相的圆锥角有关的螺旋轴的有序参数。