Natural and Magnetic Circular Dichroism From the Infrared to the UV of a Hetero[4]helicene Radical Cation.

Dithiabridged triarylamine hetero[4]helicenes are an interesting class of chiral compounds characterized by a high racemization barrier which makes them an attractive material for several applications. Their rich redox chemistry allows one to obtain radical cations stable at room temperature, that can be isolated in two configurationally stable enantiomers. While several studies have been reported on systems with transition metals possessing low-lying electronic states, the characterization of purely organic open-shell systems by VCD is still scarce. This may be due to the instability of radical-cation species and to the dark color assumed by the solution at the high concentration required by VCD. The oxidation of this molecular system shifts the first electronic transition towards the Near-IR (NIR) region, at approximately 1250 nm. By combining ECD, VCD, MCD, NIR-CD and computational methodologies rooted in density functional theory, we have investigated one molecule of this class of compounds and shed some light on the chiroptical properties accessible via redox-switch.