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

Research output: Contribution to journalArticle

8 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 - May 15 2017

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Boats
Paraquat
Paramagnetic resonance
Electronic equipment
Single crystals
Spectroscopy
X ray diffraction
Thin films
Electrons
naphthalenediimide

Keywords

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

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework. / Nguyen, Minh T.; Krzyaniak, Matthew D.; Owczarek, Magdalena; Ferris, Daniel P.; Wasielewski, Michael R; Stoddart, J. Fraser.

In: Angewandte Chemie - International Edition, Vol. 56, No. 21, 15.05.2017, p. 5795-5800.

Research output: Contribution to journalArticle

Nguyen, Minh T. ; Krzyaniak, Matthew D. ; Owczarek, Magdalena ; Ferris, Daniel P. ; Wasielewski, Michael R ; Stoddart, J. Fraser. / A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework. In: Angewandte Chemie - International Edition. 2017 ; Vol. 56, No. 21. pp. 5795-5800.
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