A Boat‐Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework. (21st April 2017)

• Record Type: Journal Article
• Authors: Nguyen, Minh T.; Krzyaniak, Matthew D.; Owczarek, Magdalena; Ferris, Daniel P.; Wasielewski, Michael R.; Stoddart, J. Fraser
• Is Part Of: Angewandte Chemie. Volume 129:Number 21(2017)
• Page Start: 5889
• Page End: 5894
• Publication Date: 2017-04-21
• Subjects: Elektronentransport -- Makrocyclen -- Molekulare Elektronik -- Organische Gerüststrukturen -- Organische Halbleiter; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201702019
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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 4+ 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 4+, 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 −4 S m −1 . 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.