Tunable Mixed-Valence Doping toward Record Electrical Conductivity in a Three-Dimensional Metal–Organic Framework

Partial oxidation of an iron-tetrazolate metal-organic framework (MOF) upon exposure to ambient atmosphere yields a mixed-valence material with single-crystal conductivities tunable over 5 orders of magnitude and exceeding 1 S/cm, the highest for a three-dimensionally connected MOF. Variable-temperature conductivity measurements reveal a small activation energy of 160 meV. Electronic spectroscopy indicates the population of midgap states upon air exposure and corroborates intervalence charge transfer between Fe²⁺ and Fe³⁺ centers. These findings are consistent with low-lying Fe³⁺ defect states predicted by electronic band structure calculations and demonstrate that inducing metal-based mixed valency is a powerful strategy toward realizing high and systematically tunable electrical conductivity in MOFs.