π-Electron Conjugation in Two Dimensions
- 3 October 2013
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 135 (44), 16585-16594
- https://doi.org/10.1021/ja408355p
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 experimentally realized 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.Keywords
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