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Published August 1, 2018 | Supplemental Material
Journal Article Open

A Mixed-Valence Superstructure Assembled from A Mixed-Valence Host-Guest Complex


Herein, we report an unprecedented mixed-valence crystal superstructure that consists of a 2:1 host–guest complex [MV⊂(CBPQT)_2]^(2/3+) [MV = methyl viologen, CBPQT = cyclobis(paraquat-p-phenylene)]. One electron is distributed statistically between three [MV⊂(CBPQT)_2]•+ composed of a total of 15 viologen units. The mixed-valence state is validated by single-crystal X-ray crystallography, which supports an empirical formula of [MV⊂(CBPQT)_2]_3·(PF_6)_2 for the body-centered cubic superstructure. Electron paramagnetic resonance provides further evidence of electron delocalization. Quantum chemistry calculations confirm the mixed-valence state in the crystal superstructure. Our findings demonstrate that precise tuning of the redox states in host–guest systems can lead to a promising supramolecular strategy for achieving long-range electron delocalization in solid-state devices.

Additional Information

© 2018 American Chemical Society. Received: May 22, 2018; Published: June 27, 2018. This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at the King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. W.-G.L. and W.A.G. were supported by NSF (EFRI-1332411). This work used the Extreme Science and Engineering Discovery Envoronment (XSEDE), which is supported by NSF (ACI-1053575). This research was also supported by the National Science Foundation under grant no. DMR-1710104 (M.R.W.). The authors declare no competing financial interest.

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