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Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐System

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With 2,1,3-benzochalcogenadiazoles C6R4N2E (E/R; E = S, Se, Te; R = H, F, Cl, Br, I) and C6H2R2N2E (E/R’; E = S, Se, Te; R = Br, I) – 10π-electron hetarenes, it is shown by CV / EPR measurements, DFT calculations, and QTAIM and ELI-D analyses that their molecular electron affinities (EAs) increase with decreasing Allen electronegativities and electron affinities of the E and non-hydrogen R (except Cl) atoms. DFT calculations for E/R + e·– → [E/R]·– electron capture reveal negative ΔG values numerically increasing with increasing atomic numbers of the E and R atoms; positive ΔS has a minor influence. It is suggested that the increased EAs are caused by more effective charge / spin delocalization in the radical anions of heavier derivatives due to contributions from diffuse (a real-space expanded) p-AOs of the heavier E and R atoms; and that this counterintuitive effect might be of the general character.

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