Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework
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paper76.pdf
Description
Accepted version
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1.3 MB
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Author(s)
Xie, Lilia S.
Sun, Lei
Wan, Ruomeng
Park, Sarah Sunah
DeGayner, Jordan A.
Hendon, Christopher H.
Dinca, Mircea
Date Issued
May 2018
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Xie, Lilia S., et al. "Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework." Journal of the American Chemical Society 140, 24 (2018): p. 7411-14 doi 10.1021/JACS.8B03604 ©2018 Author(s)
Version
Author's final manuscript
Abstract
Partial oxidation of an iron-tetrazolate metal-organic framework (MOF) upon exposure to ambient atmosphere yields a mixed-valence material with single-crystal conductivities tunable over 5 orders of magnitude and exceeding 1 S/cm, the highest for a three-dimensionally connected MOF. Variable-temperature conductivity measurements reveal a small activation energy of 160 meV. Electronic spectroscopy indicates the population of midgap states upon air exposure and corroborates intervalence charge transfer between Fe[superscript 2+] and Fe[superscript 3+] centers. These findings are consistent with low-lying Fe[superscript 3+] defect states predicted by electronic band structure calculations and demonstrate that inducing metal-based mixed valency is a powerful strategy toward realizing high and systematically tunable electrical conductivity in MOFs.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1021/JACS.8B03604
