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

Research output: Contribution to journal › Article › peer-review

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
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
Publication status	Published - 1 Aug 2018
Externally published	Yes

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@article{e2b7c97a19f54778999a9116825462e6,

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\}",

note = "Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = aug,

day = "1",

doi = "10.1021/jacs.8b05322",

language = "English",

volume = "140",

pages = "9387--9391",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

number = "30",

}

TY - JOUR

T1 - Mixed-Valence Superstructure Assembled from a Mixed-Valence Host-Guest Complex

AU - Liu, Zhichang

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.

UR - https://www.scopus.com/pages/publications/85049361626

U2 - 10.1021/jacs.8b05322

DO - 10.1021/jacs.8b05322

M3 - Article

C2 - 29949368

AN - SCOPUS:85049361626

SN - 0002-7863

VL - 140

SP - 9387

EP - 9391

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 30

ER -

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

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