A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework

Minh T. Nguyen, Matthew D. Krzyaniak, Magdalena Owczarek, Daniel P. Ferris, Michael R. Wasielewski, J. Fraser Stoddart

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10 Citations (Scopus)

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) (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.

Original languageEnglish
Pages (from-to)5795-5800
Number of pages6
JournalAngewandte Chemie - International Edition
Volume56
Issue number21
DOIs
Publication statusPublished - Jan 1 2017

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Keywords

  • electron transport
  • macrocycles
  • molecular electronics
  • organic frameworks
  • organic semiconductors

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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