Fine‐Tuning of the Sequential Self‐Assembly of Entangled Polyhedra by Exploiting the Side‐Chain Effect

Abstract The control of the sequential self‐assembly processes of highly entangled (Ag 3 L 2 ) n ( n =2,4,6,8) and Ag 21 L 12 coordination polyhedra using side‐chain effects was studied via the introduction of linear or branched side chains into the tripodal ligands. In addition to changes in the intermediate polyhedral species affording the multi‐ pathway process, disruption of the kinetic control of the sequential self‐assembly was observed, thus demonstrating the utility of steric control for the construction of 3D‐entangled molecular materials on the 5 nm scale with high molecular complexity.