We report a relatively persistent, open-shell aza-Thiahelicene with cross-conjugated electron-rich ?-system. The singly occupied molecular orbital (SOMO) energy levels of both radical cation and neutral radical of the helicene are below the highest occupied molecular orbital (HOMO) energy levels, thereby violating the Aufbau principle. The aza-Thiahelicene is prepared from β-hexathiophene by a three-step one-pot reaction, in which the pyrrole ring is constructed by two consecutive C-N bond formations. Chemical oxidation converts the helicene to its radical cation, while in the presence of base (Cs2CO3), the oxidation gives neutral aminyl radical, likely via proton dissociation from the aminium radical cation with a low pKa. Reaction of the aza-Thiahelicene with NaH provides the corresponding anion, which shows characteristic cyclic voltammetry wave at anodic peak potential Epa ? +0.2 V. Chemical oxidation of the anion with ferrocenium hexafluorophosphate at room temperature gives persistent neutral aminyl radical. Structure of the aza-Thiahelicene is supported by NMR, IR, X-ray crystallography, and cyclic voltammetry. The radical cation and neutral radical are characterized by EPR and UV-vis-NIR spectroscopies. DFT computations of the radical cation and neutral radical predict the SOMO-HOMO energy level inversion, which is supported experimentally by electrochemical data for the radical cation.
ASJC Scopus subject areas
- Colloid and Surface Chemistry