Liquid Crystal Institute and Chemical Physics Interdisciplinary Program, Kent State University, Kent, Ohio 44242, USA.
J Am Chem Soc. 2010 Dec 29;132(51):18361-6. doi: 10.1021/ja108437n. Epub 2010 Dec 2.
We report here a fast-photon-mode reversible handedness inversion of a self-organized helical superstructure (i.e., a cholesteric liquid crystal phase) using photoisomerizable chiral cyclic dopants. The two light-driven cyclic azobenzenophanes with axial chirality show photochemically reversible trans to cis isomerization in solution without undergoing thermal or photoinduced racemization. As chiral inducing agents, they exhibit good solubility, high helical twisting power, and a large change in helical twisting power due to photoisomerization in three commercially available, structurally different achiral liquid crystal hosts. Therefore, we were able to reversibly tune the reflection colors from blue to near-IR by light irradiation from the induced helical superstructure. More interestingly, the different switching states of the two chiral cyclic dopants were found to be able to induce a helical superstructure of opposite handedness. In order to unambiguously determine the helical switching, we employed a new method that allowed us to directly determine the handedness of the long-pitched self-organized cholesteric phase.
我们在此报告了一种使用光致变色手性环状掺杂剂实现自组织螺旋超结构(即胆甾相液晶)快速光频模式手性反转的方法。两种具有轴向手性的光致异构化手性环状偶氮苯在溶液中表现出光化学可逆的顺反异构化,而不会经历热或光诱导外消旋化。作为手性诱导剂,它们在三种商业可得的、结构不同的无手性液晶主体中具有良好的溶解性、高的螺旋扭曲力和由于光致异构化引起的螺旋扭曲力的较大变化。因此,我们能够通过照射诱导的螺旋超结构将反射颜色从蓝色调谐到近红外光。更有趣的是,发现两种手性环状掺杂剂的不同开关状态能够诱导具有相反手性的螺旋超结构。为了明确确定螺旋的开关,我们采用了一种新的方法,该方法允许我们直接确定长螺距自组织胆甾相的手性。