Akademik Veri Yönetim Sistemi
Molecular Physics, 2025 (SCI-Expanded, Scopus)
Cryptophane-based molecular cages represent an emerging class of supramolecular hosts with unique potential in binding environmentally relevant ions. In this work, we investigate the interaction of cryptophane-111, a compact and rigid variant, with the uranyl ion, which is of critical interest in nuclear chemistry and waste remediation. Using density functional theory (DFT), natural bond orbital (NBO) analysis, quantum theory of atoms in molecules (QTAIM), and cavity mapping via MoloVol, a detailed host–guest picture is presented. Volumetric calculations demonstrate that the internal cavity of cryptophane-111 provides a spatially well-matched environment for uranyl encapsulation. Energetic analysis reveals a favorable interaction energy of –38.78 kcal/mol, confirming stable complex formation. Encapsulation induces substantial modifications in the electronic structure of the host, including a reduction in the HOMO–LUMO gap and enhanced electrophilicity, signaling stronger orbital interactions and charge delocalization. Complementary NBO and QTAIM analyses highlight donor–acceptor contributions and weak but persistent electrostatic interactions stabilizing the system. Together, these insights suggest that cryptophane-111 functions effectively as a soft molecular trap for uranyl ions. Beyond fundamental host–guest chemistry, the findings underscore its promise in nuclear waste remediation, environmental sensing, and actinide separation technologies.