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

Liu, Zhichang and Frasconi, Marco and Liu, Wei-Guang and Zhang, Yu and Dyar, Scott M. and Shen, Dengke and Sarjeant, Amy A. and Goddard, William A., III and Wasielewski, Michael R. and Stoddart, J. Fraser (2018) A Mixed-Valence Superstructure Assembled from A Mixed-Valence Host-Guest Complex. Journal of the American Chemical Society, 140 (30). pp. 9387-9391. ISSN 0002-7863.

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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.

Item Type:Article
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URLURL TypeDescription Information
Liu, Zhichang0000-0003-3412-512X
Frasconi, Marco0000-0003-2010-175X
Liu, Wei-Guang0000-0002-6633-7795
Zhang, Yu0000-0001-8938-1927
Sarjeant, Amy A.0000-0002-1993-0406
Goddard, William A., III0000-0003-0097-5716
Wasielewski, Michael R.0000-0003-2920-5440
Stoddart, J. Fraser0000-0003-3161-3697
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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King Abdulaziz City for Science and Technology (KACST)UNSPECIFIED
Northwestern UniversityUNSPECIFIED
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Issue or Number:30
Record Number:CaltechAUTHORS:20180627-154043155
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Official Citation: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 III, Michael R. Wasielewski, and J. Fraser Stoddart Journal of the American Chemical Society 2018 140 (30), 9387-9391 DOI: 10.1021/jacs.8b05322
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:87419
Deposited By: George Porter
Deposited On:27 Jun 2018 23:00
Last Modified:03 Oct 2019 19:55

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