A computational study on the host–guest complexes of neutral bis(4-nitrophenyl)squaramide (SQ) and halide anions is reported. In the gas-phase, the calculated interaction and stabilization energies indicates a diminishing intrinsic affinity of SQ for anions from fluoride to iodide. The nature of interactions is investigated using Natural Bond Orbital (NBO), Quantum Theory of Atoms in Molecules (QTAIM) along with Energy Decomposition Analysis-Natural Orbitals for Chemical Valence (EDA-NOCV). While electrostatic interactions account for roughly 60% of the total, EDA-NOCV analysis demonstrated increasing contributions of orbital interactions from to complexes. In solution, thermodynamic cycle analyses and Gibbs free energy calculations reveal a propensity towards the formation of , taking into account the influence of solvation energies on the overall stability. The consistent trend observed in selectivity both in the gas phase and in solution suggests that changes in solvation energy do not significantly impact the stability of complexes. The findings were additionally supported by a significant correlation observed between the computed and experimental formation constants.
