Dissipative self-assembly of metal-organic complexes

Implementing dissipative processes in networks of dynamic molecules holds great promise for developing new functional behaviours. Here we report the use of trichloroacetic acid as a chemical fuel to temporarily push networks of dynamic imine-based metal complexes far from thermodynamic equilibrium, forcing them to express high free-energy complexes otherwise unfavourable under equilibrium conditions. Basic design principles were determined for the creation of such networks. Where a complex distribution of products was obtained at equilibrium, the fuel-induced rearrangement temporarily yielded a simplified output, forcing a more structured high-energy distribution of products. Where a single complex was obtained at equilibrium, the fuel-induced rearrangement temporarily modified the properties of this complex. By doing so, the mechanical properties of an helical macrocyclic complex could be temporarily altered by rearranging it into a [2]catenane.