Predicting the helical sense of Poly(phenylacetylene)s from their Electron Circular Dichroism Spectra

The calculated ECD spectrum (time-dependent density functional theory TD-DFT) for small oligomers of polyphenylacetylenes (PPAs) show a very good match with the experimental spectra of the PPA polymers, particularly with the first Cotton band associated to the helical sense of the internal polyenic backbone. This has been proven with a series of PPAs representative of cis-cisoidal, cis-transoidal, com- pressed and stretched polyene backbones, with identical or opposite internal/external rotational senses and allows the prediction of the helical sense of the internal helix of a PPA directly from its CD spectra.