Through versus Cross Electron Delocalization in Polytriacetylene Oligomers: A Computational Analysis

Abstract

Herein, we report a systematic theoretical investigation of the molecular and electronic properties of unsubstituted polytriacetylene (PTA) and iso-polytriacetylene (iso-PTA) oligomers, which are characterized by through and cross pi-conjugation pathways, respectively. The goal of the study is to compare through versus cross conjugation on the basis of the computed molecular geometries of the neutral, anionic, and cationic species, the electron affinities, ionization potentials, excitation energies, and nonlinear optical properties for oligomers up to the nonamer. Differences in the effective conjugation length are directly related to electron delocalization in cross- and through-conjugated pathways. As in the through-conjugated oligomers, that is, the PTAs, the frontier orbitals of the iso-PTA oligomers are delocalized along the entire carbon backbone, suggesting that pi-delocalization can extend through cross-linked carbon atoms. However, in contrast to the PTA oligomers, the bond lengths remain strictly constant and the reduction of the energy gap beyond the trimer is completely due to the correlation contribution. On the other hand, in the anions and cations, the bond lengths do change significantly with increasing chain length. Therefore, oxidation or reduction of the iso-PTA oligomer appears to switch on delocalization through cross-linked carbon atoms. Obviously, the effective conjugation length is specific and depends on the observable considered.