2026 Volume 87 Pages 12-17
In this study, the kinetic aspects of molecular self-assembly were revealed. The self-assembly mechanisms of metal-organic cages were investigated by experimental and numerical analyses (QASAP–NASAP), found that the emergence of quasi-reversibility of certain elementary reactions in a reaction network is the key to pathway selection in the self-assembly of M6L4 truncated tetrahedron (TT) and higher acceleration of the later stage of the self-assembly of M6L4 square-based pyramid (SP) by ReO4 – led to a very high yield. Novel strategies were developed for the formation of large metal–organic cages based on the remote geometric communication of multitopic ligands and kinetic control of the assembly of heteroleptic Pd(II)–coordination cages. It was also discovered that unusual reactivities of structurally very similar Pd4L8 interpenetrated cages that have F– and/or Cl– in their three pockets and interpreted the different reactivities based on a new index that can evaluate the suitability of anions to the pockets.
