Pick and choose: Novel cationic diaza-, azaoxo-, and dioxo[6]helicenes are readily prepared and functionalized selectively by orthogonal aromatic electrophilic and vicarious nucleophilic substitutions (see scheme). Reductions, cross-coupling, or condensation reactions introduce additional diversity and allow tuning of the absorption properties up to the near-infrared region. The diaza salts can be resolved into single enantiomers.