Decoding the ECD Spectra of Poly(phenylacetylene)s: Structural Significance

The role of the main dihedral angles in the electronic circular dichroism (ECD) spectra of poly(phenylacetylene)s (PPAs) was estimated by using time-dependent density functional theory (TD-DFT) for oligo(phenylacetylene)s (n = 12). These studies reveal that in cis-transoidal arrangements, the first Cotton effect is dominated by excitations involving molecular orbitals (MOs) mainly related to the polyene backbone. Hence, for this scaffold, the ± sign of the first Cotton effect reflects the P/M helical sense of the internal helix of the polymer. However, in cis-cisoidal arrangements, contribution of MOs in the polyene and the aryl rings of the PPA backbone produce the first Cotton effect band. As a result, two different ECD signatures with three or four alternating Cotton effects can be produced depending on the sign of the ω₁ and ω₃ dihedral angles which determine the helical sense of the polyene (ω₁) and the relative orientation of the aryl ring toward the polyene (ω₃), respectively. Thus, on the one hand, if ω₁ and ω₃ rotate in opposite directions, a CD with three alternating Cotton effects is observed, where the sign of first Cotton correlates with the P/M helical sense of the polyene. On the other hand, if ω₁ and ω₃ rotate in the same direction, a CD signature with four alternating Cotton effects is produced where the information relative to the P/M helical sense of the polyene is contained in the second Cotton effect.