Organic Chemistry of Graphene: The Diels–Alder Reaction

AbstractHerein, by using dispersion‐corrected density functional theory, we investigated the Diels–Alder chemistry of pristine and defective graphene. Three dienes were considered, namely 2,3‐dimethoxy‐1,3‐butadiene (DMBD), 9‐methylanthracene (9MA), and 9,10‐dimethylanthracene (910DMA). The dienophiles that were assayed were tetracyanoethylene (TCNE) and maleic anhydride (MA). When pristine graphene acted as the dienophile, we found that the cycloaddition products were 47–63 kcal mol−1 less stable than the reactants, thus making the reaction very difficult. The presence of Stone–Wales translocations, 585 double vacancies, or 555‐777 reconstructed double vacancies did not significantly improve the reactivity because the cycloaddition products were still located at higher energy than the reactants. However, for the addition of 910DMA to single vacancies, the product showed comparable stability to the separated reactants, whereas for unsaturated armchair edges the reaction was extremely favorable. With regards the reactions with dienophiles, for TCNE, the cycloaddition product was metastable. In the case of MA, we observed a reaction product that was less stable than the reactants by