Fuel-Controlled Reassembly of Metal-Organic Architectures

Many examples exist of biological self-assembled structures that restructure in response to external stimuli, then return to their previous state over a defined time scale, but most synthetic investigations so far have focused on systems that switch between states representing energetic minima upon stimulus application. Here we report an approach in which triphenylphosphine is used as a chemical fuel to maintain Cu^I-based self-assembled metallosupramolecular architectures for defined periods of time. This method was used to exert control over the threading and dethreading of the ring of a pseudorotaxane's axle, as well as to direct the uptake and release of a guest from a metal-organic host. Management of the amount of fuel and catalyst added allowed for time-dependent regulation of product concentration.