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Updated: Jul 21, 2025

Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Reducing Systematic Uncertainty in Computed Redox Potentials for Aqueous Transition-Metal-Substituted
Jake A Thompson1, Rebeca González-Cabaleiro2, Laia Vilà-Nadal1
1School of Chemistry, University of Glasgow, Glasgow G12 8QQ, U.K.
Abstract:
Polyoxometalates have attracted significant interest owing to their structural diversity, redox stability, and functionality at the nanoscale. In this work, density functional theory calculations have been employed to systematically study the accuracy of various exchange-correlation functionals in reproducing experimental redox potentials, U0Red in [PW11M(H2O)O39] M = Mn(III/II), Fe(III/II), Co(III/II), and Ru(III/II). U0Red calculations for [PW11M(H2O)O39] were calculated using a conductor-like screening model to neutralize the charge in the cluster. We explicitly located K+ counterions which induced positive shifting of potentials by > 500 mV. This approximation improved the reproduction of redox potentials for K[XW11M(H2O)O39] M = Mn(III/II)/Co(III/II). However, uncertainties in U0Red for K[PW11M(H2O)O39] M = Fe(III/II)/Ru(III/II) were observed because of the over-stabilization of the ion-pairs. Hybrid functionals exceeding 25% Hartree-Fock exchange are not recommended because of large uncertainties in ΔU0Red attributed to exaggerated proximity of the ion-pairs. Our results emphasize that understanding the nature of the electrode and electrolyte environment is essential to obtain a reasonable agreement between theoretical and experimental results.
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