Electrostatic–Polarization Interactions of Aerogen: Quantum Mechanical and Topological Directives From Solvation to Supramolecular Encapsulation

The paradoxical formation of supramolecular assemblies involving heavy noble gases and polar or aromatic molecules challenges classical chemical bonding paradigms. This study utilizes DFT, EDA, and topological assessments (QTAIM, ELF) to evaluate the noncovalent interactions of noble gases with molecules like H 2 O, NH 3 , CH 4 , delocalized π‐surfaces, and within a rigid cavitand. Our computational and crystallographic analyses reveal that these assemblies are not governed by orbital‐driven charge transfer. Instead, they are strictly dictated by induced electrostatic polarization and London dispersion forces. Thermodynamic stability scales directly with the central atom’s electrostatic gradient (H 2 O > NH 3 > CH 4 > C 6 H 6 ) and the noble gas’s atomic polarizability. The interaction strength rigorously scales with atomic polarizability (Ne < Ar < Kr < Xe), transitioning from electrostatically dominated. Notably, topological mapping identifies an argon anomaly, where Ar achieves optimal localized electron density at the interaction boundary by balancing valence polarizability against Pauli repulsion. Furthermore, we demonstrate that spatial confinement of xenon within a macrocyclic cavitand, calix[4]resorcinarene, mechanically compresses its diffuse electron cloud, inducing a highly directional positive electrostatic pole at its apex. This anisotropic polarization transforms the chemically inert gas into a detailed, structure‐directing supramolecular anchor, providing a fundamental predictive framework for advanced crystal engineering.