Mandle Richard J, Goodby John W
Department of Chemistry, University of York, York, YO10 5DD, UK.
Angew Chem Int Ed Engl. 2018 Jun 11;57(24):7096-7100. doi: 10.1002/anie.201802881. Epub 2018 May 8.
The twist-bend modulated nematic liquid-crystal phase exhibits formation of a nanometre-scale helical pitch in a fluid and spontaneous breaking of mirror symmetry, leading to a quasi-fluid state composed of chiral domains despite being composed of achiral materials. This phase was only observed for materials with two or more mesogenic units, the manner of attachment between which is always linear. Non-linear oligomers with a H-shaped hexamesogen are now found to exhibit both nematic and twist-bend modulated nematic phases. This shatters the assumption that a linear sequence of mesogenic units is a prerequisite for this phase, and points to this state of matter being exhibited by a wider range of self-assembling structures than was previously envisaged. These results support the double helix model of the TB phase as opposed to the simple heliconical model. This new class of materials could act as low-molecular-weight surrogates for cross-linked liquid-crystalline elastomers.
扭曲-弯曲调制向列相液晶在流体中呈现纳米级螺旋螺距的形成以及镜面对称性的自发破缺,尽管由非手性材料组成,但仍导致由手性畴构成的准流体状态。该相仅在具有两个或更多介晶单元的材料中观察到,且这些介晶单元之间的连接方式始终是线性的。现在发现具有H形六介晶元的非线性低聚物同时呈现向列相和扭曲-弯曲调制向列相。这打破了介晶单元线性序列是该相的先决条件这一假设,并表明这种物质状态可由比先前设想的更广泛的自组装结构呈现。这些结果支持扭曲-弯曲相的双螺旋模型,而非简单的螺旋模型。这类新型材料可作为交联液晶弹性体的低分子量替代物。