A Boat‐Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework

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) (CBPQT4+ 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 CBPQT4+, 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. Organische Elektronik: Ein tetrakationischer Makrocyclus bestehend aus zwei Naphthalindiimid(NDI)‐Einheiten und vier Pyridiniumringen wurde synthetisiert und auf sein Potential als organischer Halbleiter untersucht. Der Einbau der NDI‐Einheiten in die Cyclobis(paraquat‐p‐phenylen)‐Struktur führt zu einem Makrocyclus mit bootförmiger Konformation, der sich zu einem supramolekularen Netzwerk mit ultragroßen Poren und Halbleitereigenschaften zusammenfügt.