Electronic Structures and Chiroptical Properties of Post-functionalized Helicene Quinones.

The synthesis of redox-active p- and o-quinones 2-phenylamino-4-phenylimino[6]helicene-1-one 1, 2-phenylamino[6]-helicene-1,4-dione 2, and 4-phenyl[6]helicene-1,2-dione 3 in their enantiopure forms by post-functionalization of (P)- and (M)-1,2-dimethoxy[6]helicene is presented. Structural characterization in solution and in the solid state was accomplished by 2D NMR spectroscopy methods and X-ray diffraction analysis, respectively. Interpretation of electrochemical redox data was accompanied by a detailed orbital picture, derived from DFT calculations. The electronic structures of compounds 1-3 were investigated by UV/Vis and electronic circular dichroism (ECD) spectroscopy, complemented by TD-DFT calculations. Quinones 1-3 were chemically reduced to study the EPR signatures of their respective radical anions. DFT methods were used for the atom assignment of the hyperfine coupling constants. The results are discussed within the context of electrochromic chiral switches and molecular recognition.