Tuning Aromaticity, Stability and Radicaloid Character of Periacenes by Chemical BN Doping

ABSTRACT

In this work, the stability, aromaticity and radical character of pristine and eleven BN‐doped armchair 5 and zigzag 5, 6, and 7 periacenes, were chosen for studying the effect of different doping schemes to stabilize the periacene, and to direct the open‐shell density into specific regions of the PAH sheets. Ab initio multireference methods and different DFT functionals were used to analyze the singlet triplet (ST) energy. Moreover, a range of descriptors were used to characterize the open‐shell character and aromaticity of the different doped structures. The overall results provide a good overview of the efficiency of the different doping topologies. In general, because of the closed‐shell character of the borazine doping units, the role of the doping is to reduce the strong open‐shell character of the pristine periacenes. Substitutions along the zigzag edges has a significant effect while doping along the armchair edges is not significant.