With the aim of designing graftable calix[6]tren‐based receptors, calix[6]trenamides decorated with an appended functional arm were synthesized through [1+1] macrocyclization reactions between calix[6]trisamines and NTA‐lysine derivatives. NMR spectroscopy and ESI‐MS studies showed that one of these calix[6]trenamides, 5, behaves as a unique heteroditopic receptor towards charged or neutral species. Notably, it can selectively bind contact ammonium fluoride salts through a highly cooperative process. In addition, acid–base control of its binding properties was clearly evidenced. This second generation of graftable receptors opens new perspectives in the design of sensors for charged or neutral species.
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