Tautomerism‐Coupled Self‐Assembly and Transformations of Iminopyrrole Metallacages

Four discrete metallacages were obtained from the condensation of 2,5‐diformylpyrrole and tren in the presence of Zn(II). The structures differed in nuclearity, size, and symmetry, with the number of templating cations playing a key role in defining the properties of the architecture. The diiminopyrrole coordination motif, a fundamental structural feature of assemblies, undergoes tautomerization in certain cases, yielding an iminoaminoazafulvene, which alters the assembly. The controlled interconversion between bi‐, tetra‐, and dodecanuclear cages was achieved through simple stimuli, highlighting the dynamic nature of these assemblies.