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.
Original language | English (US) |
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Pages (from-to) | 9387-9391 |
Number of pages | 5 |
Journal | Journal of the American Chemical Society |
Volume | 140 |
Issue number | 30 |
DOIs | |
State | Published - Aug 1 2018 |
ASJC Scopus subject areas
- Chemistry(all)
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry
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CCDC 985866: Experimental Crystal Structure Determination
Liu, Z. (Contributor), Frasconi, M. (Contributor), Liu, W. (Contributor), Zhang, Y. (Contributor), Dyar, S. M. (Contributor), Shen, D. (Contributor), Sarjeant, A. A. (Contributor), Goddard, W. A. (Contributor), Wasielewski, M. R. (Contributor), Stoddart, J. F. (Contributor) & Wasielewski, M. R. (Contributor), Cambridge Crystallographic Data Centre, 2018
DOI: 10.5517/ccdc.csd.cc122w45, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc122w45&sid=DataCite
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