Li Chunji, Cho Joonil, Yamada Kuniyo, Hashizume Daisuke, Araoka Fumito, Takezoe Hideo, Aida Takuzo, Ishida Yasuhiro
Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Hongo, Bunkyo, Tokyo 113-8656, Japan.
RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan.
Nat Commun. 2015 Sep 29;6:8418. doi: 10.1038/ncomms9418.
Helical nanostructures have attracted continuous attention, not only as media for chiral recognition and synthesis, but also as motifs for studying intriguing physical phenomena that never occur in centrosymmetric systems. To improve the quality of signals from these phenomena, which is a key issue for their further exploration, the most straightforward is the macroscopic orientation of helices. Here as a versatile scaffold to rationally construct this hardly accessible structure, we report a polymer framework with helical pores that unidirectionally orient over a large area (∼10 cm(2)). The framework, prepared by crosslinking a supramolecular liquid crystal preorganized in a magnetic field, is chemically robust, functionalized with carboxyl groups and capable of incorporating various basic or cationic guest molecules. When a nonlinear optical chromophore is incorporated in the framework, the resultant complex displays a markedly efficient nonlinear optical output, owing to the coherence of signals ensured by the macroscopically oriented helical structure.
螺旋纳米结构一直备受关注,不仅作为手性识别和合成的介质,还作为研究在中心对称系统中从未出现过的有趣物理现象的基元。为了提高这些现象的信号质量,这是进一步探索它们的关键问题,最直接的方法是使螺旋宏观取向。在这里,作为一种通用的支架来合理构建这种难以获得的结构,我们报道了一种具有螺旋孔的聚合物框架,其在大面积(约10平方厘米)上单向取向。该框架通过交联在磁场中预组织的超分子液晶制备,化学性质稳定,带有羧基官能团,能够容纳各种碱性或阳离子客体分子。当将非线性光学发色团引入该框架时,由于宏观取向的螺旋结构确保了信号的相干性,所得复合物显示出明显高效的非线性光学输出。