Liquid-Crystalline Perylene Bisimide Derivatives Bearing an Azacrown Ether Ring Complexing with Alkaline metal ions
Liquid-Crystalline Perylene Bisimide Derivatives Bearing an Azacrown Ether Ring Complexing with Alkaline metal ions
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含氮杂冠醚环与碱金属离子络合的液晶苝双酰亚胺衍生物
DOI：
10.1039/d1qm01542g
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
M. Funahashi
中科院分区：
文献类型：
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作者：
T. Taga;S. Takaoka;S. Uemura;M. Funahashi
对于电化学应用，需要具有离子传导性的可溶液加工的氧化还原活性材料。此外，薄膜应不溶于电解质溶液。我们合成了一种带有氮杂冠醚结构的苝酰亚胺衍生物。在室温下，苝酰亚胺衍生物表现出矩形有序的柱状相。该化合物与三氟甲磺酸锂和三氟甲磺酸钠以1：1的摩尔比形成液晶复合物，而在与三氟甲磺酸钾以1：1的摩尔比的混合物中发生相分离。 这种液晶性的二萘嵌苯双酰亚胺衍生物即使在非极性有机溶剂中也是可溶的，这是由于通过旋涂方法产生的庞大的环四硅氧烷环和薄膜。原子力显微镜研究显示，纤维状纳米结构的复合物的膜的表面上，表明超分子柱状结构的形成。该化合物的旋涂薄膜可以通过暴露于三氟甲磺酸的蒸气上经由原位开环聚合过程而不溶解。不溶薄膜表现出红色中性和紫色二价阴离子状态之间的电致变色。
For electrochemical applications, solution-processable redox-active materials with ion conductivity are required. Moreover, the thin films should be insolubilized for the usage with electrolyte solutions. We synthesized a perylene bisimide derivative bearing an azacrown ether moiety. The perylene bisimide derivative exhibited a rectangular ordered columnar phase at room temperature. This compound formed liquid crystalline complexes with lithium triflate and sodium triflate in a molar ratio of 1 : 1 while phase separation occurred in the mixture with potassium triflate in a molar ratio of 1 : 1. This liquid crystalline perylene bisimide derivative was soluble even in non-polar organic solvents, due to bulky cyclotetrasiloxane rings and thin films being produced by the spin-coating method. AFM studies revealed fibrous nanostructures on the surfaces of the films of the complexes, indicating the formation of supramolecular columnar structures. The spin-coated thin film of this compound could be insolubilized by an exposure on the vapors of trifluoromethanesulfonic acid via an in situ ring-opening polymerization process. The insolubilized thin film exhibited electrochromism between red neutral and violet dianion states.