Is iron unique in promoting electrical conductivity in MOFs?

Abstract

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 Fe^3+/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.