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 Ag6 L4 metallocage was developed. Induced by SbF6 - anions, both kinetically controlled [Ag3 L2 (SbF6 )3 ]n and thermodynamically controlled [Ag2 L2 (SbF6 )2 ]n can be reassembled from discrete Ag6 L4 (SbF6 )6 metallocages at 30 °C, and increasing the temperature to 40 °C results in selective inhibition of the kinetic product. Under the influence of BF4 - anions, dynamic Ag6 L4 (BF4 )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.