Dataset for theTriple para-Functionalized Cations and Neutral Radicals of Enan-tiopure Diaza [4]Helicenes

Modulation of absorbance and emission is key for the design of chiral chromophores. For dyes to be of practical value in (chir)optical applications, they must also absorb and/or emit (circularly polarized) light over a wide spectral window, and often toward near infrared. In a series of derivatives bridging triaryl methyl and helicene domains, we have achieved by late-stage functionalization the regioselective triple introduction of para electron-donating or electron-withdrawing substituents. Extended tuning of electronic (e.g., E1/2red –1.50 V → –0.68 V) and optical (e.g., emission covering from 550 to 850 nm) properties is achieved for the cations and neutral radicals; the latter compounds being easily prepared by mono electron reductions under electrochemical or chemical conditions. While luminescence quantum yields can be increased up to 70% in the cationic series, strong Cotton effects are obtained for certain radicals at low energies (λabs ~ 700-900 nm) with gabs values above 10-3. The open-shell electronic nature of the radicals was further characterized by EPR revealing an important spin density delocalization that contributes to their persistence