Helicene Quinones: Redox-Triggered Chiroptical Switching and Chiral Recognition of the Semiquinone Radical Anion Lithium Salt by Electron Nuclear Double Resonance Spectroscopy

We present the synthesis and characterization of enantiomerically pure [6]helicene o-quinones (P)-(+)-1 and (M)-(-)-1 and their application to chiroptical switching and chiral recognition. (P)-(+)-1 and (M)-(-)-1 each show a reversible one-electron reduction process in their cyclic voltammogram, which leads to the formation of the semiquinone radical anions (P)-()-1(center dot-) and (M)-(-)-1(center dot-), respectively. Spectroelectrochemical ECD measurements give evidence of the reversible switching between the two redox states, which is associated with large differences of the Cotton effects [Delta(Delta epsilon)] in the UV and visible regions. The reduction of (+/-)-1 by lithium metal provides [Li+{(+/-)-1(center dot-)}], which was studied by EPR and ENDOR spectroscopy to reveal substantial delocalization of the spin density over the helicene backbone. DFT calculations demonstrate that the lithium hyperfine coupling A(Li-7) in [Li+{(+/-)-1(center dot-)}] is very sensitive to the position of the lithium cation. On the basis of this observation, chiral recognition by ENDOR spectroscopy was achieved by complexation of [Li+{(P)-(+)-1(center dot-)}] and [Li+{(M)-(-)-1(center dot-)}] with an enantiomerically pure phosphine oxide ligand.