Selective Metal‐ion Complexation of a Biomimetic Calix[6]arene Funnel Cavity Functionalized with Phenol or Quinone

In the biomimetic context, many studies have evidenced the importance of the 1(st) and 2(nd) coordination sphere of a metal ion for controlling its properties. Here, we propose to evaluate a yet poorly explored aspect, which is the nature of the cavity that surrounds the metal labile site. Three calix[6]arene‐based aza‐ligands are compared, that differ only by the nature of cavity walls, anisole, phenol or quinone (L(OMe) , L(OH) and L(Q) ). Monitoring ligand exchange of their Zn(II) complexes evidenced important differences in the metal ion relative affinities for nitriles, halides or carboxylates. It also showed a possible sharp kinetic control on both, metal ion binding and ligand exchange. Hence, this study supports the observations reported on biological systems, highlighting that the substitution of an amino‐acid residue of the enzyme active site, at remote distance of the metal ion, can have strong impacts on metal ion lability, substrate/product exchange or selectivity.