1,2,4,5‐Tetrakis(tetramethylguanidino)‐3,6‐diethynyl‐benzenes: Fluorescent Probes, Redox‐Active Ligands and Strong Organic Electron Donors

In this work, the change of reactivity induced by the introduction of two para‐ethynyl substituents (CCSi(iPr)(3) or CCH) to the organic electron‐donor 1,2,4,5‐tetrakis(tetramethylguanidino)‐benzene is evaluated. The redox‐properties and redox‐state dependent fluorescence are evaluated, and dinuclear Cu(I) and Cu(II) complexes synthesized. The Lewis‐acidic B(C(6)F(5))(3) substitutes the proton of the ethynyl −CCH groups to give new anionic −CCB(C(6)F(5))(3) (−) substituents, leading eventually to a novel dianionic strong electron donor in its diprotonated form. Its two‐electron oxidation with dioxygen in the presence of a copper catalyst yields the first redox‐active guanidine that is neutral (instead of cationic) in its oxidized form.