Highlight on the solution processes occurring on silver(i)-assembling porphyrins in the presence of an excess of silver salt.

Coordination cages obtained upon complexation of pyridyl functionalized porphyrins by Ag+ disassemble when overtaking a 1 : 2 stoichiometric amount of silver salt. An excess of Ag+ then leads to unusual chemical processes, here analyzed in detail, which permanently transform the monomeric porphyrins. The observed processes, discussed with reference to model compounds devoid of polyether substituted pyridyl residues, evidence a peculiar reactivity for meso 2,6-dimethylphenyl substituted porphyrins.