[en] Full text: Inspired by recent progress in the synthesis of cluster assembled solids, and the theoretical description of globally delocalized electronic structure of nanoscale building blocks – superatoms – we address the question to what extent the three new materials [Co₆Se₈(PEt₃)₆][C₆₀]₂, [Cr₆Te₈(PEt₃)₆][C₆₀]₂, and [Ni₉Te₆(PEt₃)₈]C₆₀, upon forming bulk compounds, imitate atomic analogues. The concept of superatoms for describing atom-imitating clusters is very intriguing since it allows chemists to apply chemical intuition – a useful tool for predicting new materials – when it comes to inter-cluster reactions. Thus, we systematically study the lattice structure, the intercluster binding, and the electronic structure by density functional theory and assess their superatomic features. We show that collective properties emerge upon bulk formation, which promotes arguments for the formation of solids in which the constituent clusters have a superatomic character, allowing for solid-state concepts to become relevant. Finally, we present principles for the design of novel assemblies created from tunable superatoms and methods for the prediction of their electronic properties. We also propose an extension of the superatomic concept to include tunable transition metal clusters, which have long been neglected but which allow for the incorporation of tunable magnetic states. (author)