Cation-dependent intrinsic electrical conductivity in isostructural tetrathiafulvalene-based microporous metal-organic frameworks

Sarah S. Park, Eric R. Hontz, Lei Sun, Christopher H. Hendon, Aron Walsh, Troy Van Voorhis, Mircea Dincə

Research output: Contribution to journalArticle

147 Citations (Scopus)

Abstract

Isostructural metal-organic frameworks (MOFs) M2(TTFTB) (M = Mn, Co, Zn, and Cd; H4TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S···S interaction defined by neighboring TTF cores, which inversely correlates with the ionic radius of the metal ions. The larger cations cause a pinching of the S···S contact, which is responsible for better orbital overlap between pz orbitals on neighboring S and C atoms. Density functional theory calculations show that these orbitals are critically involved in the valence band of these materials, such that modulation of the S···S distance has an important effect on band dispersion and, implicitly, on the conductivity. The Cd analogue, with the largest cation and shortest S···S contact, shows the largest electrical conductivity, σ = 2.86 (±0.53) × 10-4 S/cm, which is also among the highest in microporous MOFs. These results describe the first demonstration of tunable intrinsic electrical conductivity in this class of materials and serve as a blueprint for controlling charge transport in MOFs with π-stacked motifs.

Original languageEnglish
Pages (from-to)1774-1777
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number5
DOIs
Publication statusPublished - 2015 Feb 11

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Electric Conductivity
Cations
Positive ions
Metals
Blueprints
Valence bands
Density functional theory
Metal ions
Charge transfer
Demonstrations
Modulation
Single crystals
Atoms
Ions
tetrathiafulvalene

All Science Journal Classification (ASJC) codes

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

Cite this

Park, Sarah S. ; Hontz, Eric R. ; Sun, Lei ; Hendon, Christopher H. ; Walsh, Aron ; Van Voorhis, Troy ; Dincə, Mircea. / Cation-dependent intrinsic electrical conductivity in isostructural tetrathiafulvalene-based microporous metal-organic frameworks. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 5. pp. 1774-1777.
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Cation-dependent intrinsic electrical conductivity in isostructural tetrathiafulvalene-based microporous metal-organic frameworks. / Park, Sarah S.; Hontz, Eric R.; Sun, Lei; Hendon, Christopher H.; Walsh, Aron; Van Voorhis, Troy; Dincə, Mircea.

In: Journal of the American Chemical Society, Vol. 137, No. 5, 11.02.2015, p. 1774-1777.

Research output: Contribution to journalArticle

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