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

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348 Scopus citations


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
Issue number5
StatePublished - 11 Feb 2015

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© 2015 American Chemical Society.


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