Length Ratio‐Driven Configurational Modulation of Heteroleptic Pd ₆ L ₆ L’ ₆ Cages

Abstract

Abstract 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 Pd 6 L 6 L' 6 cages by systematically varying the ligand length ratio ( r ). Although theoretical analysis suggests that these Pd 6 L 6 L' 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.