Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks
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Dinca_Cation-dependent.pdf
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Author(s)
Hendon, Christopher H.
Walsh, Aron
Park, Sarah Sunah
Hontz, Eric Richard
Sun, Lei
Van Voorhis, Troy
Dinca, Mircea
Date Issued
January 2015
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Park, Sarah S. et al. “Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal–Organic Frameworks.” Journal of the American Chemical Society 137.5 (2015): 1774–1777. © 2015 American Chemical Society
Version
Final published version
Abstract
Isostructural metal–organic frameworks (MOFs) M[subscript 2](TTFTB) (M = Mn, Co, Zn, and Cd; H[subscript 4]TTFTB = 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[subscript –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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ja512437u
