ELECTRONIC-STRUCTURE CALCULATIONS ON HELICENES - CONCERNING THE CHIRALITY OF HELICALLY TWISTED AROMATIC SYSTEMS

CNDO/S calculations including configuration interaction of up to 300 s ingly excited states have been performed on the MMP2 and PM3 optimized geometries of [n]-helicenes, with n from 3 to 9. Oscillator and rotat ory strengths have been calculated for all states down to 200 nm, with generally good agreement in the long wavelength regions. The computed data are analyzed on the basis of a four-orbital model yielding two f orbidden L and two allowed B states. The latter ones including signs c orrelate with two high intensity absorptions of opposite signs observe d in the spectra of all helicenes except the smallest one. The descrip tion in terms of tangential and radial transition dipoles provides a p hysical picture of the excited states. It is shown that the -,+ patter n of these bands is conclusive evidence for the M-helical absolute con figuration of these compounds.