Length Ratio‐Driven Configurational Modulation of Heteroleptic Pd6L6L'6 Cages

Biomolecular configurational modulation is essential for maintaining the stability and functionality of biological systems. Drawing inspiration from this natural phenomenon, we present a strategy to modulate the configurations of heteroleptic Pd6L6L'6 cages by systematically varying the ligand length ratio (r). Although theoretical analysis suggests that these Pd6L6L'6 assemblies could adopt up to 48 possible configurational isomers, we successfully modulated the thermodynamic preference between two dominant configurations (Type‐A and Type‐B) by implementing energetic differentiation through careful optimization of r. Specifically, the system exclusively forms Type‐A cages at r = 1.0, whereas Type‐B becomes the predominant configuration when r ≥ 1.4. Control experiments demonstrate that the introduction of bulky steric groups does not induce configuration changes. This research offers valuable insights and serves as a useful reference for the design and configurational modulation of heteroleptic cages.