Ionic Radius Dependent Kinetic Behavior for the Self‐Assemblyand Chiral Amplification of Lanthanide Tetrahedral Cages

Comprehensive Summary Understanding the kinetic process during the self‐assembly and chiral amplification of metal‐organic polyhedra (MOPs) is critical for the rational preparation of chiral MOPs. Herein, we report the ionic radius dependent kinetic processes for the self‐assembly and chiral amplification of Ln 4 L 4 ‐type (Ln, Lanthanides; L, ligand) lanthanide tetrahedral cages. The chiral Eu 4 ( L R ) 4 tetrahedral cage is structurally characterized by nuclear magnetic resonance (NMR), electrospray ionization time‐of‐flight mass spectrometry (ESI‐TOF‐MS), and single crystal X‐ray diffraction. Kinetic study on the stereo‐controlled self‐assembly of circularly polarized luminescence (CPL)‐active Ln 4 ( L R ) 4 (Ln = La III , Pr III and Eu III ) tetrahedra manifests that the larger ionic radius of Ln leads to faster assembly rates. Mixed‐ligand cage assembly experiments with chiral L R / S , achiral L ac and Ln (1 : 3 : 4 molar ratio) reveal that the self‐assembly and chiral amplification occur synchronously for the La III and Pr III cages, while two distinct steps, i.e ., first self‐assembly and then chiral amplification, are observed for the Eu III cage. Such distinct kinetic behavior is attributed to different ligands exchange rates among the mixed‐ligand Ln 4 L 4 cages. This work provides fundamental guidance for fabrication and property‐optimization of chiral lanthanide‐based molecular materials.