Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208, USA.
Angew Chem Int Ed Engl. 2017 May 15;56(21):5795-5800. doi: 10.1002/anie.201702019. Epub 2017 Apr 21.
We report the synthesis of a tetracationic macrocycle which contains two N,N'-bis(methylene)naphthalenediimide units inserted in between the pyridinium rings of the bipyridinium units in cyclobis(paraquat-p-phenylene) (CBPQT or "blue box") and describe the investigation of its potential use in materials for organic electronics. The incorporation of the two naphthalenediimide (NDI) units into the constitution of CBPQT , not only changes the supramolecular properties of the tetracation in the solid state, but also has a profound influence on the electrochemical and electronic behavior of the resulting tetracationic macrocycle. In particular, the solid-state (super)structure, investigated by single-crystal X-ray diffraction, reveals the formation of a three-dimensional (3D) supramolecular framework with ca. 2.8 nm diameter one-dimensional (1D) hexagonal channels. Electrochemical studies on solid-state thin films of the macrocycle show that they exhibit semiconducting properties with a redox-conductivity of up to 7.6×10 S m . Moreover, EPR and ENDOR spectroscopies show that charge is equally shared between the NDIs within the one-electron reduced state of the NDI-based macrocycle on the time scale of these techniques.
我们报告了一种四阳离子大环的合成，该大环包含两个 N,N'-双（亚甲基）萘二酰亚胺单元，插入到双吡啶单元的吡啶环之间，这些双吡啶单元位于环双（对醌-对亚苯基）（CBPQT 或“蓝盒”）中，并描述了其在有机电子材料中的潜在用途。将两个萘二酰亚胺（NDI）单元引入 CBPQT 的结构中，不仅改变了四阳离子在固态下的超分子性质，而且对所得四阳离子大环的电化学和电子行为也有深远的影响。特别是，通过单晶 X 射线衍射研究的固态（超）结构，揭示了形成具有约 2.8nm 直径一维（1D）六方孔的三维（3D）超分子框架。大环的固态薄膜的电化学研究表明，它们表现出半导体性质，其氧化还原电导率高达 7.6×10S m。此外，EPR 和 ENDOR 光谱学表明，在 NDI 基大环的单电子还原态下，NDI 之间的电荷在这些技术的时间尺度上是平均分配的。
