Finely Resolved Threshold for the Sharp M₁₂L₂₄/M₂₄L₄₈ Structural Switch in Multi‐Component M_<i>n</i>L_2<i>n</i> Polyhedral Assemblies: X‐ray, MS, NMR, and Ultracentrifugation Analyses

Abstract

In the self-assembly of M(n)L(2n) polyhedra, the bend angle (θ) of the divalent ligand components determines the final structure. The threshold for the sharp structural switch between M12L24 and M24L48 was finely resolved to within just 4° by demonstrating the exclusive formation of M12L24 cuboctahedra or M24L48 rhombicuboctahedra from two similar ligands with θ values of 130° and 134°. This sharp structural switch was fully confirmed by X-ray crystallography, mass spectrometry, NMR spectroscopy, and ultracentrifugation analyses.