Stepwise and concerted dissociative electron transfer onto a σ*-type orbital in polybrominated aromatics

•The σ*CBr-based LUMO for polybrominated aromatics•Aromatic halides undergo concerted sticky dissociative ET.•Strong charge–dipole interaction (Ar⋯Br−)solv pairs formed upon reduction.•Radical anions of C6Br6− and C6Br5Cl− are σ*-type.

Convolution analysis of voltammetric data along with DFT calculations shows that the studied pentabromophenyl ethers undergo concerted dissociative electron transfer onto a σ*CBr-type orbital. Hexabromobenzene and chloropentabromobenzene form σ* radical anions upon reduction.

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