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
N1 - Funding Information:
This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdul-Aziz City for Science and Technology (KACST) and Northwestern University (NU). The authors would like to thank both KACST and NU for their continued support of this research. This work was supported by the U.S. National Science Foundation under grant no. CHE-1565925 (M.R.W.).
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 -