Tuning of the Electronic Properties of Armchair Graphene Nanoribbons through Functionalization: Theoretical Study of (1)Δg O2 Border Addition.

We report the results of a DFT study of the border oxidation by (1) Δg O2 of molecular models of armchair graphene nanoribbons (a-GNRs). The aim of this work is to propose a new method, as an alternative or complementary method to the tuning of the size, to modify the electronic properties of a-GNRs. Here, we investigate modification of the HOMO and LUMO energies, which are some of the most important parameters to be controlled in the design of organic electronic devices. We study the oxidation reaction mechanism of medium-size polycyclic aromatic hydrocarbons, mimicking the stiffness and reactivity of a-GNRs. Thermodynamics and kinetics indicate that the reaction should bring about a decoration of the borders with vicinal dialdehyde groups. We also study the effect of this oxidation on the HOMO and LUMO energies of two series of molecular models of a-GNRs with increasing lengths. The results suggest that the oxidized a-GNRs should present LUMO energies lowered by 0.3-0.5 eV with respect to the original material, whereas the HOMO energies are barely lowered.