π‑Electron Conjugation in Two Dimensions

Abstract

Organic oligomers and polymers with extended π-conjugation are the fundamental building blocks of organic electronic devices. Novel routes are being explored to create tailor-made organic materials, and recent progress in organic chemistry and surface chemistry has led to the synthesis of planar 2D polymers. Here we show how extending π-conjugation in the second dimension leads to novel materials with HOMO–LUMO gaps smaller than in 1D polymers built from the same parent molecular repeat unit. Density functional theory calculations on <i>experimentally realized</i> 2D polymers grant insight into HOMO–LUMO gap contraction with increasing oligomer size and show fundamental differences between 1D and 2D “band gap engineering”. We discuss how the effects of cross-conjugation and dihedral twists affect the electronic gaps