Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 137, Issue 5, Pages 1774-1777Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja512437u
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (U.S. DOE-BES) [DE-SC0006937]
- NSF GRFP [1122374]
- Center for Excitonics, an Energy Frontier Research Center - U.S. DOE-BES [DE-SC0001088]
- David and Lucille Packard Foundation
- EPSRC [EP/L00202]
- U.S. Department of Energy (DOE) [DE-SC0006937] Funding Source: U.S. Department of Energy (DOE)
- EPSRC [EP/L000202/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/L000202/1] Funding Source: researchfish
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Isostructural metalorganic frameworks (MOFs) M-2(TTFTB) (M = Mn, Co, Zn, and Cd; H4TTFTB = tetrathiafulvalene tetrabenzoate) exhibit a striking correlation between their single-crystal conductivities and the shortest S center dot center dot center dot 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 center dot center dot center dot S contact, shows the largest electrical conductivity, pi = 2.86 (+/- 0.53) X 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 pi-stacked motifs.
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