Density functional theory study of crown ether–magnesium complexes: from a solvated ion to an ion trap

Metal ion detection rests on host–guest recognition. We propose a theoretical protocol for designing an optimal trap for a desired metal cation. A host for magnesium ions was sought for among derivatives of crown ethers 12-crown-4, 15-crown-5, and 18-crown-6. Mg–crown complexes and their hydrated counterparts with water molecules bound to the cation were optimized using density functional theory. Based on specific geometric criteria, Interacting quantum atoms analysis and density functional theory-based molecular dynamics of Mg–crown complexes immersed in water, crown ethers for optimal accommodation of Mg²⁺ in aqueous solution were identified. Selectivity of the chosen crowns towards Na⁺, K⁺, and Ca²⁺ ions is addressed.