Development of Anisotropically Ion and Mass-Transporting Materials through Self-Organization of Ionic Liquids

制造具有层次有序结构的功能分子材料是下一代的重要课题之一。使用自组织过程是制备此类材料的通用工具。特别是电子和离子传输有机材料，由于其在分子器件、信息和能量传输领域的潜在应用而受到人们的关注。在离子传输材料中，我们重点研究了离子液体，即具有高离子导电性的有机熔盐。本研究的目的是通过对咪唑盐进行化学修饰得到的离子液晶的自组织来开发低维离子传输材料。本文报道了两类各向异性离子传输材料：(1)一维（1D）离子传输柱状液晶；(2)二维离子传输聚合物薄膜。我们设计并制备了由亲脂部分和咪唑部分组成的扇形块分子。这些分子表现出柱状液晶相。在这些结构中，主音部分自组织到柱的中心。柱通过机械剪切在宏观上平行于玻璃表面排列。平行于柱状轴的离子电导率高于垂直于柱状轴的离子电导率。首次实现了柱状液晶材料的各向异性一维离子传导。(2)二维离子传输聚合物薄膜制备了具有可聚合基团的密晶液晶咪唑盐，获得了二维离子导电的机械稳定聚合物薄膜。这些在近晶A相的分子在玻璃表面自发地形成了各向同性单畴。通过光聚合得到了具有层状纳米结构的自立聚合物薄膜。它们表现出各向异性的二维tonic电导率。少

The fabrication of functional molecular materials forming hierarchical ordered structures is one of important subjects for the next generation. Use of self-organization processes is a versatile tool for the preparation of such materials. In particular, electron and ion-transporting organic materials have attracted attention due to their potential applications in the fields of molecular devices and transportation of information and energy. Among the ion-transporting materials, we focused on ionic liquids that are organic molten salts showing high ionic conductivities. The objective in this study is to develop low-dimensionally ion-transporting materials through self-organization of ionic liquid crystals obtained by the chemical modification of imidazolium salts. Here we report on two types of anisotropic ion-transporting materials : (1)one-dimensionally (1D) ion-transporting columnar liquid crystals ; (2)two-dimensionally (2D) ion-transporting polymeric films.(1)1D ion-transporting colu … More mnar liquid crystalsWe designed and prepared fan-shaped block molecules comprising lipophilic part and imidazolium moieties. These molecules exhibited columnar liquid crystalline phases. In these structures, the tonic parts self-organized into the center of columns. The columns were macroscopically aligned parallel to the glass surface by mechanical shearing. The ionic conductivities parallel to the columnar axis were higher than those perpendicular to the axis. For the first time, anisotropic 1D ion conduction was achieved for columnar liquid crystalline materials.(2)2D ion-transporting polymeric filmsSmectic liquid crystalline imidazolium salts having polymerizable groups were prepared to obtain 2D ion-conductive mechanically stable polymeric films. These molecules in the smectic A phase spontaneously formed homeotropic monodomains on the glass surface. Self-standing polymeric films with layered nanostructures were obtained by photopolymerization of the oriented materials. They showed anisotropic 2D tonic conductivities. Less