Issue 6, 2017

Is iron unique in promoting electrical conductivity in MOFs?


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.

Graphical abstract: Is iron unique in promoting electrical conductivity in MOFs?

Supplementary files

Article information

Article type
Edge Article
13 Feb 2017
18 Apr 2017
First published
20 Apr 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 4450-4457

Is iron unique in promoting electrical conductivity in MOFs?

L. Sun, C. H. Hendon, S. S. Park, Y. Tulchinsky, R. Wan, F. Wang, A. Walsh and M. Dincă, Chem. Sci., 2017, 8, 4450 DOI: 10.1039/C7SC00647K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity