Room Temperature Metallic Conductivity in a Metal-Organic Framework Induced by Oxidation

Andrew J. Clough, Nicholas M. Orchanian, Jonathan M. Skelton, Abbey J. Neer, Sebastian A. Howard, Courtney A. Downes, Louis F.J. Piper, Aron Walsh, Brent C. Melot, Smaranda C. Marinescu

Research output: Contribution to journalArticle

Abstract

Metal-organic frameworks (MOFs) containing redox active linkers have led to hybrid compounds exhibiting high electrical conductivity, which enables their use in applications in electronics and electrocatalysis. While many computational studies predict two-dimensional (2D) MOFs to be metallic, the majority of experiments show decreasing conductivity on cooling, indicative of a gap in the electronic band structure. To date, only a handful of MOFs have been reported that exhibit increased electrical conductivity upon cooling indicative of a metallic character, which highlights the need for a better understanding of the origin of the conductivity. A 2D MOF containing iron bis(dithiolene) motifs was recently reported to exhibit semiconducting behavior with record carrier mobility. Herein, we report that high crystallinity and the elimination of guest species results in an iron 2,3,6,7,10,11-tripheylenehexathiolate (THT) MOF, FeTHT, exhibiting a complex transition from semiconducting to metallic upon cooling, similar to what was shown for the analogous CoTHT. Remarkably, exposing the FeTHT to air significantly influences the semiconducting-to-metallic transition temperature (100 to 300 K) and ultimately results in a material showing metallic-like character at, and above, room temperature. This study indicates these materials can tolerate a substantial degree of doping that ultimately results in charge delocalization and metallic-like conductivity, an important step toward enabling their use in chemiresistive sensing and optoelectronics.

Original languageEnglish
Pages (from-to)16323-16330
Number of pages8
JournalJournal of the American Chemical Society
Volume141
Issue number41
DOIs
Publication statusPublished - 2019 Oct 16

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Metals
Oxidation
Temperature
Electric Conductivity
Cooling
Iron
Electrocatalysis
Transition Temperature
Carrier mobility
Optoelectronic devices
Band structure
Superconducting transition temperature
Oxidation-Reduction
Electronic equipment
Air
Doping (additives)
Experiments

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Clough, A. J., Orchanian, N. M., Skelton, J. M., Neer, A. J., Howard, S. A., Downes, C. A., ... Marinescu, S. C. (2019). Room Temperature Metallic Conductivity in a Metal-Organic Framework Induced by Oxidation. Journal of the American Chemical Society, 141(41), 16323-16330. https://doi.org/10.1021/jacs.9b06898
Clough, Andrew J. ; Orchanian, Nicholas M. ; Skelton, Jonathan M. ; Neer, Abbey J. ; Howard, Sebastian A. ; Downes, Courtney A. ; Piper, Louis F.J. ; Walsh, Aron ; Melot, Brent C. ; Marinescu, Smaranda C. / Room Temperature Metallic Conductivity in a Metal-Organic Framework Induced by Oxidation. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 41. pp. 16323-16330.
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Clough, AJ, Orchanian, NM, Skelton, JM, Neer, AJ, Howard, SA, Downes, CA, Piper, LFJ, Walsh, A, Melot, BC & Marinescu, SC 2019, 'Room Temperature Metallic Conductivity in a Metal-Organic Framework Induced by Oxidation', Journal of the American Chemical Society, vol. 141, no. 41, pp. 16323-16330. https://doi.org/10.1021/jacs.9b06898

Room Temperature Metallic Conductivity in a Metal-Organic Framework Induced by Oxidation. / Clough, Andrew J.; Orchanian, Nicholas M.; Skelton, Jonathan M.; Neer, Abbey J.; Howard, Sebastian A.; Downes, Courtney A.; Piper, Louis F.J.; Walsh, Aron; Melot, Brent C.; Marinescu, Smaranda C.

In: Journal of the American Chemical Society, Vol. 141, No. 41, 16.10.2019, p. 16323-16330.

Research output: Contribution to journalArticle

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AU - Clough, Andrew J.

AU - Orchanian, Nicholas M.

AU - Skelton, Jonathan M.

AU - Neer, Abbey J.

AU - Howard, Sebastian A.

AU - Downes, Courtney A.

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AU - Melot, Brent C.

AU - Marinescu, Smaranda C.

PY - 2019/10/16

Y1 - 2019/10/16

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Clough AJ, Orchanian NM, Skelton JM, Neer AJ, Howard SA, Downes CA et al. Room Temperature Metallic Conductivity in a Metal-Organic Framework Induced by Oxidation. Journal of the American Chemical Society. 2019 Oct 16;141(41):16323-16330. https://doi.org/10.1021/jacs.9b06898