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Controllable Reassembly of a Dynamic Metallocage: From Thermodynamic Control to Kinetic Control
Luyao Liu1, Guangxun Lyu1, Caiping Liu1
1State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.
Abstract:
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.
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