Cation-Anion Arrangement Patterns in Self-Assembled Pd₂L₄ and Pd₄L₈ Coordination Cages

Compounds featuring one-dimensional regular arrangements of stacked metal complexes and alternating [cation-anion]_∞ sequences have raised considerable interest owing to their peculiar electronic and optical properties as well as guest inclusion capabilities. While traditional ways to realize these structural motifs rely on crystalline compounds, exclusively existing in the solid state, recent progress in the area of metal-mediated supramolecular self-assembly allows for the rational synthesis of structurally well-defined short stretches of stacked metal complexes and cation-anion arrangements. Therefore, metal cations, counteranions, and suitably designed organic bridges are allowed to self-assemble in solution. While the bridges can be designed as cross-linkers to yield extended two- or three-dimensional networks such as layered materials, metal-organic frameworks (MOFs), or porous coordination polymers (PCPs), they can also be tailored to lead to discrete nanoscopic objects. Supramolecular helicates, grids, and knots belong to this class of compounds, and a particularly interesting subfamily are coordination cages and capsules, which possess nanosized cavities with the ability to encapsulate guest molecules. Here, we focus on coordination cages consisting of two or more square-planar Pd(II) or Pt(II) metal cations, bridged by banana-shaped bis-monodentate pyridyl ligands that encapsulate various guest molecules, usually anions, in their cavities. Monoanions as well as dianions with localized or delocalized charges can be bound with remarkable complementarity between cage and guest in terms of size and shape. We show how dimerization of the prototypical [Pd₂L₄] cages into their interpenetrated dimers [Pd₄L₈] leads to an increase in cavity number from one to three while the cavity volume decreases. Usually, all three pockets of these double cages are filled with monoanions such as BF₄^- or Cl^-, thus leading to well-defined linear [Pd-anion]₃Pd stacks, as observed by X-ray studies. The ligand-based mechanical coupling of the linearly aligned cavities leads to interesting effects concerning guest encapsulation cooperativity, such as allosteric binding and triggered sequential uptake. While most of the so far reported coordination cages consist of only a single type of ligand, recent advances in rational assembly strategies allow for high-yielding syntheses of structurally defined multicomponent architectures by integrative self-sorting mechanisms. One family of heteroleptic [Pd₂L₂L'₂] cages whose formation is based on shape-complementarity between two different ligands, L and L', is introduced. Furthermore, the implementation of ligand-based functions such as redox activity, photochromic behavior, specific binding sites, chirality, and catalytic activity allows us to study systems with properties far beyond basic structural features. We showcase selected examples of self-assembled cages whose guest uptake or even overall structural integrity is reversibly switched by light or small molecules with potential application in stimuli responsive materials (e.g., for sequestration of pollutants or stabilization of reactive compounds) up to functional nanosystems (e.g., diagnostic devices or supramolecular catalysts) and molecular machines.