Coordination-Directed Self-Assembly of M₁₂L₂₄ Nanocage: Effects of Kinetic Trapping on the Assembly Process

We demonstrate the spontaneous formation of spherical complex M₁₂L₂₄, which is composed of 12 palladium ions and 24 bidentate ligands, by molecular dynamics simulations. In contrast to our previous study on the smaller M₆L₈ cage, we found that the larger M₁₂L₂₄ self-assembly process involves noticeable kinetic trapping at lower nuclearity complexes, <i>e.g.</i>, M₆L₁₂, M₈L₁₆, and M₉L₁₈. We also found that the kinetic trapping behaviors sensitively depend on the bend angle of ligands and the metal–ligand binding strength. Our results show that these kinetic effects, that have generally been neglected, are important factor in self-assembly structure determination of larger complexes as M₁₂L₂₄ in this study