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 language | English |
|---|---|
| Pages (from-to) | 5795-5800 |
| Number of pages | 6 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 56 |
| Issue number | 21 |
| DOIs | |
| Publication status | Published - May 15 2017 |
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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 journal › Article
}
TY - JOUR
T1 - A Boat-Shaped Tetracationic Macrocycle with a Semiconducting Organic Framework
AU - Nguyen, Minh T.
AU - Krzyaniak, Matthew D.
AU - Owczarek, Magdalena
AU - Ferris, Daniel P.
AU - Wasielewski, Michael R
AU - Stoddart, J. Fraser
PY - 2017/5/15
Y1 - 2017/5/15
N2 - 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.
AB - 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.
KW - electron transport
KW - macrocycles
KW - molecular electronics
KW - organic frameworks
KW - organic semiconductors
UR - http://www.scopus.com/inward/record.url?scp=85018563561&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85018563561&partnerID=8YFLogxK
U2 - 10.1002/anie.201702019
DO - 10.1002/anie.201702019
M3 - Article
C2 - 28429421
AN - SCOPUS:85018563561
VL - 56
SP - 5795
EP - 5800
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 21
ER -