Abstract The capability of resorcinarenes to bind anions within the alkyl feet at the lower rim has been exploited as the starting point for developing a new cavitand able to engulf contact ion pairs of primary ammonium salts in chlorinated solvents with association constants (K ass) in the range of 10 3–10 4 M− 1. Methylene bridges were introduced into the upper rim to freeze the resorcinarene in the cone conformation with the four H down protons ...