Triggering Redox Activity in a Thiophene Compound: Radical Stabilization and Coordination Chemistry

The synthesis, metalation, and redox properties of an acyclic bis(iminothienyl)methene L⁻ are presented. This π‐conjugated anion displayed pronounced redox activity, undergoing facile one‐electron oxidation to the acyclic, metal‐free, neutral radical L ^. on reaction with FeBr₂. In contrast, the reaction of L⁻ with CuI formed the unique, neutral Cu₂I₂( L ^.) complex of a ligand‐centered radical, whereas reaction with the stronger oxidant AgBF₄ formed the metal‐free radical dication L ^.2+.