Tuning the photophysical and chiroptical properties of [4]helicene-diketopyrrolopyrroles

Synthesis and functionalization of diketopyrrolo[3,4-c]pyrrole (DPP) derivatives containing chiral groups able to induce a strong chiral perturbation of the DPP core are still a challenging task. We report in this work the straightforward preparation of four bis([4]helicene)-DPP and bis([4]thiahelicene)-DPP dyes upon the condensation of 2-CN-[4](thia)helicene precursors, followed by their N-alkylation by nucleophilic substitution (compounds 9-11) or by a Mitsunobu-type strategy (compound 12). Compound 12, which contains sec-phenylethyl groups attached to the nitrogen atoms, has been obtained as (R,R) and (S,S) enantiomers. The four DPP-helicenes are luminescent in solution, while the N-benzyl (10) and N-sec-phenethyl (12) are emissive in the solid state as well. The chiroptical properties of compound 12 in solution and in the solid state indicate a strong chiral perturbation provided by the alpha-stereogenic centres, in spite of the stereodynamic nature of the [4]helicene flanking units.

Automated summary

This study reports the synthesis and functionalization of diketopyrrolo[3,4-c]pyrrole (DPP) derivatives containing chiral groups. Four bis([4]helicene)-DPP and bis([4]thiahelicene)-DPP dyes were prepared by condensation and N-alkylation reactions. Compound 12, with sec-phenylethyl groups attached to the nitrogen atoms, was obtained as enantiomers. The chiroptical properties of compound 12 indicate a strong chiral perturbation despite the stereodynamic nature of the flanking units.