From cationic to anionic Al12B and Al13 clusters. Aromatic characteristics for intermediate superatomic species

Abstract

Al13- remains a prototypical superatomic cluster, featuring 40-cluster electrons (ce), fulfilling a closed shell electronic structure with spherical aromatic characteristics. Here, we evaluated intermediate counterparts, given by Al13+ (38-ce) and neutral Al13 (39-ce), which can be controlled by the use of different n- and p-type organic substrates, exhibiting a decreased spherical aromatic behavior. In addition, the boron-doped isoelectronic counterparts show similar characteristics. For both cationic and neutral clusters, a contrasting magnetic behavior is observed upon different orientations of the external field, in line with the decrease in spherical aromatic characteristics, resulting in a variation of the inherent magnetic anisotropy. Moreover, despite the decrease in spherical aromaticity, their characteristics remain, leading to these intermediate superatomic clusters being also depicted as stable building blocks toward the formation of molecular-based materials, offering prototypical examples of how superatomic clusters behave after interaction with substrates.