Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework

Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework

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-tempera...

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Bibliographic Details
Main Authors: Xie, Lilia S., Sun, Lei, Wan, Ruomeng, Park, Sarah Sunah, DeGayner, Jordan A., Hendon, Christopher H., Dinca, Mircea
Other Authors: Massachusetts Institute of Technology. Department of Chemistry
Format: Article
Language:English
Published: American Chemical Society (ACS) 2020
Online Access:https://hdl.handle.net/1721.1/126154
Description
Summary: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.

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