Identifying the metal ions that optimize charge transport and charge density in metal-organic frameworks is critical for systematic improvements in the electrical conductivity in these materials. In this work, we measure the electrical conductivity and activation energy for twenty different MOFs pertaining to four distinct structural families: M2(DOBDC)(DMF)2 (M = Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+); H4DOBDC = 2,5-dihydroxybenzene-1,4-dicarboxylic acid; DMF = N,N-dimethylformamide), M2(DSBDC)(DMF)2 (M = Mn2+, Fe2+; H4DSBDC = 2,5-disulfhydrylbenzene-1,4-dicarboxylic acid), M2Cl2(BTDD)(DMF)2 (M = Mn2+, Fe2+, Co2+, Ni2+; H2BTDD = bis(1H-1,2,3-Triazolo[4,5-b],[4′,5′-i]dibenzo[1,4]dioxin), and M(1,2,3-Triazolate)2 (M = Mg2+, Mn2+, Fe2+, Co2+, Cu2+, Zn2+, Cd2+). This comprehensive study allows us to single-out iron as the metal ion that leads to the best electrical properties. The iron-based MOFs exhibit at least five orders of magnitude higher electrical conductivity and significantly smaller charge activation energies across all different MOF families studied here and stand out materials made from all other metal ions considered here. We attribute the unique electrical properties of iron-based MOFs to the high-energy valence electrons of Fe2+ and the Fe3+/2+ mixed valency. These results reveal that incorporating Fe2+ in the charge transport pathways of MOFs and introducing mixed valency are valuable strategies for improving electrical conductivity in this important class of porous materials.
Bibliographical noteFunding Information:
All experimental work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (U.S. DOE-BES, Award DE-SC0006937). M. D.Thanks 3 M, the Sloan Foundation, and the Research Corporation for Science Advancement (Cottrell Scholar Program) for non-Tenured faculty funds and the MISTI-Belgium fund for travel support. We thank Prof. S. J. Lippard for use of the Mssbauer spectrometer, Dr M. A. Minier for help with collecting preliminary 57Fe Mssbauer spectra, and Dr D. Sheberla and A. W. Stubbs for helpful discussions. S. S. P. is partially supported by a NSF GRFP (Award No. 1122374). A. W. is supported by the Royal Society, the EPSRC (Grant EP/M009580/1) and the ERC (Grant 277757). The computational work was facilitated by access to the UK National Supercomputer, ARCHER (EPSRC Grant EP/L000202) and access to the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant ACI-1053575
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