Controllable Reassembly of a Dynamic Metallocage: From Thermodynamic Control to Kinetic Control

A temperature‐ and anion‐induced coordination‐driven self‐assembly system based on a dynamic Ag 6 L 4 metallocage was developed. Induced by SbF 6 − anions, both kinetically controlled [Ag 3 L 2 (SbF 6 ) 3 ] n and thermodynamically controlled [Ag 2 L 2 (SbF 6 ) 2 ] n can be reassembled from discrete Ag 6 L 4 (SbF 6 ) 6 metallocages at 30 °C, and increasing the temperature to 40 °C results in selective inhibition of the kinetic product. Under the influence of BF 4 − anions, dynamic Ag 6 L 4 (BF 4 ) 6 metallocages self‐assemble into the thermodynamically controlled polycage at 25 °C, and lowing the temperature to 0 °C leads to selective inhibition of the thermodynamic product. Thus, both kinetically and thermodynamically controlled assembly processes in a dynamic system can be selectively driven by suitable external stimuli.