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Understanding the Reactivity of Planar Polycyclic Aromatic Hydrocarbons: Towards the Graphene Limit |
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| Authors: | Yago García‐Rodeja Prof. Dr. Miquel Solà Dr. Israel Fernández |
| Affiliation: | 1. Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Complutense, Madrid, Spain;2. Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, Girona, Spain;3. (+34)?913944310 |
| Abstract: | The Diels–Alder reactivity of maleic anhydride towards the bay regions of planar polycyclic aromatic hydrocarbons was explored computationally in the DFT framework. The process becomes more and more exothermic and the associated activation barriers become lower and lower when the size of the system increases. This enhanced reactivity follows an exponential behavior that reaches its maximum for systems having 18–20 benzenoid rings in their structures. This peculiar behavior was analyzed in detail by using the activation strain model of reactivity in combination with energy decomposition analysis. The influence of the change in the aromaticity of the polycyclic compound during the process on the respective activation barriers was also studied. |
| Keywords: | activation strain model cyclization density functional calculations polycycles polycyclic aromatic hydrocarbons |