Unraveling the flexible aromaticity of C₁₃H₉^+/0/-: a 2D superatomic-molecule theory

Phenalenyl (C₁₃H₉) is the smallest triangular unit of a graphene nanosheet, and has been experimentally verified to be stable in radical (C₁₃H₉˙), cationic (C₁₃H₉⁺), and anionic (C₁₃H₉^-) states. All these three species feature high symmetry and stability as well as delocalized π electrons, a visible sign of aromaticity, but their aromatic origin remains a challenge. This work reports new chemical insights into the π electrons of C₁₃H₉^+/0/- and deciphers their aromaticity using a recently emerged two-dimensional (2D) superatomic-molecule theory. 12π-C₁₃H₉⁺, 13π-C₁₃H₉˙, and 14π-C₁₃H₉^- are seen as triangular 2D superatomic molecules ^◊O₃, ^◊O₃^-, and ^◊O₃^2-, respectively, where ^◊O denotes a 2D benzenoid superatom bearing 4 π electrons. Visualized superatomic Lewis structures show that each ^◊O can dynamically adjust its π electrons to satisfy the superatomic sextet rule of benzene via superatomic lone pairs and covalent bonds. C₁₃H₉^+/0/- are representatives of adaptive aromaticity in the 2D superatomic-molecule system, exhibiting flexible π electronic structures to achieve shell-closure. Moreover, we specially adopt a progressive methodology to study the evolution of 2D periodic materials, by applying this theory to the similar family of C₆H₃N₇, C₁₈H₆N₂₂ and graphitic carbon nitride (g-C₃N₄) crystals, and meanwhile accounting for the special stability of g-C₃N₄. This work enriches 2D superatomic bonding chemistry and provides a useful strategy to design new 2D functional nanostructured materials.