Al₁₃⁻ and B@Al₁₂⁻ superatoms on a molecularly decorated substrate

Aluminum nanoclusters (Al_n NCs), particularly Al₁₃⁻ (n = 13), exhibit superatomic behavior with interplay between electron shell closure and geometrical packing in an anionic state. To fabricate superatom (SA) assemblies, substrates decorated with organic molecules can facilitate the optimization of cluster–surface interactions, because the molecularly local interactions for SAs govern the electronic properties via molecular complexation. In this study, Al_n NCs are soft-landed on organic substrates pre-deposited with n-type fullerene (C₆₀) and p-type hexa-tert-butyl-hexa-peri-hexabenzocoronene (HB-HBC, C₆₆H₆₆), and the electronic states of Al_n are characterized by X-ray photoelectron spectroscopy and chemical oxidative measurements. On the C₆₀ substrate, Al_n is fixed to be cationic but highly oxidative; however, on the HB-HBC substrate, they are stably fixed as anionic Al_n⁻ without any oxidations. The results reveal that the careful selection of organic molecules controls the design of assembled materials containing both Al₁₃⁻ and boron-doped B@Al₁₂⁻ SAs through optimizing the cluster–surface interactions.