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A series of 22-membered unclosed cryptands end-capped with intra-annular methyl (1), phenyl (2), p-tert-butylphenyl (3), and p-nitrophenyl (4) amide substituents (lariat arm) were synthesized to elucidate the effect of steric and electronic factors on their anion recognition behavior. The 1H NMR titrations in DMSO-d6 with 0.5% water reveal enhanced selectivity for H2PO4- vs Cl- and PhCO2-. The para-attachment of the electron-withdrawing nitro group (-NO2 vs -H and -t-Bu) was found to increase anion-binding affinity, whereas the steric bulki