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

Zhichang Liu; Marco Frasconi; Wei Guang Liu; Yu Zhang; Scott M. Dyar; Dengke Shen; Amy A. Sarjeant; William A. Goddard; Michael R. Wasielewski; J. Fraser Stoddart

doi:10.1021/jacs.8b05322

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

Zhichang Liu^*, Marco Frasconi, Wei Guang Liu, Yu Zhang, Scott M. Dyar, Dengke Shen, Amy A. Sarjeant, William A. Goddard, Michael R. Wasielewski, J. Fraser Stoddart

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article

4 Scopus citations

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)
Pages (from-to)	9387-9391
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	140
Issue number	30
DOIs	https://doi.org/10.1021/jacs.8b05322
State	Published - Aug 1 2018

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ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

Cite this

Liu, Z., Frasconi, M., Liu, W. G., Zhang, Y., Dyar, S. M., Shen, D., Sarjeant, A. A., Goddard, W. A., Wasielewski, M. R., & Stoddart, J. F. (2018). Mixed-Valence Superstructure Assembled from a Mixed-Valence Host-Guest Complex. Journal of the American Chemical Society, 140(30), 9387-9391. https://doi.org/10.1021/jacs.8b05322

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title = "Mixed-Valence Superstructure Assembled from a Mixed-Valence Host-Guest Complex",

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.",

author = "Zhichang Liu and Marco Frasconi and Liu, {Wei Guang} and Yu Zhang and Dyar, {Scott M.} and Dengke Shen and Sarjeant, {Amy A.} and Goddard, {William A.} and Wasielewski, {Michael R.} and Stoddart, {J. Fraser}",

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doi = "10.1021/jacs.8b05322",

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Mixed-Valence Superstructure Assembled from a Mixed-Valence Host-Guest Complex. / 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.

In: Journal of the American Chemical Society, Vol. 140, No. 30, 01.08.2018, p. 9387-9391.

Research output: Contribution to journal › Article

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AU - Frasconi, Marco

AU - Liu, Wei Guang

AU - Zhang, Yu

AU - Dyar, Scott M.

AU - Shen, Dengke

AU - Sarjeant, Amy A.

AU - Goddard, William A.

AU - Wasielewski, Michael R.

AU - Stoddart, J. Fraser

PY - 2018/8/1

Y1 - 2018/8/1

N2 - 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.

AB - 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.

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10.1021/jacs.8b05322