The Intricate Structural Chemistry of M^II_2<i>n</i>L_<i>n</i>‑Type Assemblies

The reaction of <i>cis</i>-blocked, square-planar M^II complexes with tetratopic N-donor ligands is known to give metallasupramolecular assemblies of the formula M_2<i>n</i>L_<i>n</i>. These assemblies typically adopt barrel-like structures, with the ligands paneling the sides of the barrels. However, alternative structures are possible, as demonstrated by the recent discovery of a Pt₈L₄ cage with unusual gyrobifastigium-like geometry. To date, the factors that govern the assembly of M^II_2<i>n</i>L_<i>n</i> complexes are not well understood. Herein, we provide a geometric analysis of M_2<i>n</i>L_<i>n</i> complexes, and we discuss how size and geometry of the ligand is expected to influence the self-assembly process. The theoretical analysis is complemented by experimental studies using different <i>cis</i>-blocked Pt^II complexes and metalloligands with four divergent pyridyl groups. Mononuclear metalloligands gave mainly assemblies of type Pt₈L₄, which adopt barrel- or gyrobifastigium-like structures. Larger assemblies can also form, as evidenced by the crystallographic characterization of a Pt₁₀L₅ complex and a Pt₁₆L₈ complex. The former adopts a pentagonal barrel structure, whereas the latter displays a barrel structure with a distorted square orthobicupola geometry. The Pt₁₆L₈ complex has a molecular weight of more than 23 kDa and a diameter of 4.5 nm, making it the largest, structurally characterized M_2<i>n</i>L_<i>n</i> complex described to date. A dinuclear metalloligand was employed for the targeted synthesis of pentagonal Pt₁₀L₅ barrels, which are formed in nearly quantitative yields