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Mixed-Valence Superstructure Assembled from a Mixed-Valence Host–Guest Complex

Author:
Liu, Zhichang, Frasconi, Marco, Liu, Wei-Guang, Zhang, Yu, Dyar, Scott M., Shen, Dengke, Sarjeant, Amy A., Goddard, William A., Wasielewski, Michael R., Stoddart, J. Fraser
Source:
Journal of the American Chemical Society 2018 v.140 no.30 pp. 9387-9391
ISSN:
1520-5126
Subject:
X-ray diffraction, chemistry, electron paramagnetic resonance spectroscopy, paraquat
Abstract:
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·(PF₆)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.
Agid:
6079154