Plenates: Anion‐Dependent Self‐Assembly of the Pyrrole Cage Encapsulating Silver(I) Clusters

The self-assembly of 2,5-diformylpyrrole, tris(2-aminoethyl)amine, and silver(I) yielded, depending on the size and basicity of the anion, new cascade complexes or plenates, that is, cryptates incorporating Agnn+ clusters. The nature of the product was counterion-dependent, and its formation was either driven by cascade anion binding or by argentophilic interactions stabilizing the cluster within the cavity. The reaction of plenates with tetrabutylammonium halides resulted in the protonation-coupled replacement of the Ag33+ with anion(s), yielding cascade cryptates.