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光诱导的含手性掺杂剂的手性液晶的重组:连接分子异构化和织构旋转

Photoinduced reorganization of motor-doped chiral liquid crystals: bridging molecular isomerization and texture rotation.

作者信息

Bosco Alessandro, Jongejan Mahthild G M, Eelkema Rienk, Katsonis Nathalie, Lacaze Emmanuelle, Ferrarini Alberta, Feringa Ben L

机构信息

Dipartimento di Scienze Chimiche, Università di Padova, Via Marzolo 1, 35131 Padova, Italy.

出版信息

J Am Chem Soc. 2008 Nov 5;130(44):14615-24. doi: 10.1021/ja8039629. Epub 2008 Oct 8.

Abstract

We recently reported that the photoisomerization of molecular motors used as chiral dopants in a cholesteric liquid crystal film induces a rotational reorganization which can be observed by optical microscopy and produces the motion of microscopic objects placed on top of the film (Feringa, B. L.; et al. Nature 2006, 440, 163; J. Am. Chem. Soc. 2006, 128, 14397). The mechanism underlying the mesoscopic manifestation of the molecular process was not fully understood, and here we present a joint theoretical and experimental investigation, which provides a detailed insight into the mechanism of texture rotation. This description allows us to identify the interplay between the chemical structure of the chiral dopant and the material properties of the liquid crystal host, and to quantify their role in the observed dynamic phenomenon. We have found that a crucial role is played by the hybrid anchoring of the liquid crystal, with the director parallel to the substrate and perpendicular to the interface with air; in this configuration an almost unperturbed cholesteric helix, with its axis normal to the substrate, is present in most of the film, with strong deformations only close to the free interface. The texture rotation observed in the experiment reflects the rotation of the director during the unwinding of the cholesteric helix, produced by the change in shape of the chiral dopant under photoisomerization. The rotational reorganization is controlled by the photochemical process, via the coupling between the chirality of the dopant and the elastic properties of the liquid crystal host.

摘要

我们最近报道,用作胆甾相液晶膜手性掺杂剂的分子马达的光异构化会引发旋转重组,这可以通过光学显微镜观察到,并能使置于膜表面的微观物体产生运动(费林加,B. L. 等人,《自然》,2006年,440卷,163页;《美国化学会志》,2006年,128卷,14397页)。分子过程的介观表现背后的机制尚未完全理解,在此我们进行了一项理论与实验相结合的研究,该研究对手性纹理旋转的机制提供了详细的见解。这种描述使我们能够确定手性掺杂剂的化学结构与液晶主体材料特性之间的相互作用,并量化它们在观察到的动态现象中的作用。我们发现液晶的混合锚定起着关键作用,指向矢平行于基板且垂直于与空气的界面;在这种配置下,膜的大部分区域存在一个几乎未受干扰的胆甾相螺旋,其轴垂直于基板,仅在靠近自由界面处有强烈变形。实验中观察到的纹理旋转反映了在胆甾相螺旋解缠过程中指向矢的旋转,这是由光异构化下手性掺杂剂形状的变化所产生的。旋转重组由光化学过程控制,通过掺杂剂的手性与液晶主体弹性特性之间的耦合实现。

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