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Updated: Oct 8, 2026

Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Electron self-exchange kinetics in two average-valence dicopper cryptates
J L Coyle1, H Elias, E Herlinger
1School of Chemistry, Queens University Belfast, Belfast BT9 5AG, UK.
Abstract:
Electron self-exchange rates, reported for two average-valence dicopper cryptates are, at around 10(5) M-1 s-1, at the high end of the range for small-molecule model compounds. The cross-exchange reaction rate, and those for oxidation with [Co(ox)3]3-, are consistent with an outer-sphere reaction mechanism. Despite the necessity for copper-copper bond making and breaking in the course of redox for one of the cryptates, the self-exchange rate is not decreased relative to the other cryptate, showing that this step is not rate limiting.
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