Superatomic-Based Ion−π Interactions

Atomic-based ion-π interactions (A-IPIs) play a fundamental role across diverse fields, such as molecular recognition, catalytic reactions, and functional materials assembly. However, the limited variety of available elements restricts the tunability of these interactions. Considering the diversity of superatomic species, in this work, we propose superatomic-based ion-π interactions (S-IPIs), in which superatoms replace atoms and interact with graphene fragments as substrates. First-principles calculations reveal that in S-IPIs, superatoms can maintain their structural stability and exhibit charge transfer behaviors dominated by electronegativity similar to A-IPIs. More importantly, properties such as interaction strength and chemical reactivity of S-IPI complexes can be modulated by altering the type and electronic configuration of superatoms, effectively expanding the traditional ion-π interaction. Our findings open up a pathway for the development of fundamental research and practical applications of ion-π interactions based on artificial elemental superatoms.