3 years ago

A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework

A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework
Minh T. Nguyen, Michael R. Wasielewski, J. Fraser Stoddart, Matthew D. Krzyaniak, Magdalena Owczarek, Daniel P. Ferris
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. Organic electronics: A tetracationic macrocyle containing two naphthalenediimide (NDI) units and four pyridinium rings was synthesized and investigated for its potential use as an organic semiconductor. The incorporation of the NDI units into the constitution of cyclobis(paraquat-p-phenylene) has resulted in a macrocyle that exhibits a boat-shape conformation and assembles into an ultralarge-pore supramolecular framework with semiconducting properties.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702019

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