Cooperative Anion‐π and C‐H‐Cl Interactions in Multifunctional Naphthalene‐Based Receptors for Chloride Recognition: Cage‐size Modulation Through Substitution Patterns

This study introduces a novel approach for chloride recognition utilizing multifunctional naphthalene‐based receptors. By strategically modifying the substitution patterns on tetrafluoropyridines, a series of new receptors with customized cavities and enhanced binding capabilities were developed. Density functional theory (DFT) calculations and experimental studies combining NMR spectroscopy and mass spectrometry confirmed the efficacy of these receptors in capturing chloride ions. The relative chloride affinity order determined experimentally is in agreement with DFT predictions. The synergistic effect of anion‐π and C‐H…Cl interactions, mediated by the TFP groups, played a crucial role in achieving high binding affinity. This work provides valuable insights for designing future anion receptors with improved performance.