Technological watch

Synthetic stimuli responsive supramolecular polymers attract increasing interest for their ability to mimic the unique properties of natural assemblies. Here we focus on the well?studied benzene?1,3,5?tricarboxamide (BTA) motif, and substitute it with two (S)?3,7?dimethyloctyl groups and an azobenzene photoswitch. We demonstrate the UV ( ? = 365 nm) induced depolymerisation of the helical hydrogen?bonded polymers in methylcyclohexane (MCH) through circular dichroism and UV?vis spectroscopy in dilute solution (15 ?M), and NMR and iPAINT super?resolution microscopy in concentrated solution (300 ?M). Repeated depolymerisation can be reversed without degradation by irradiating at ? = 455 nm. Molecular dynamics simulations show that the most energetically favourable configuration for these polymers in MCH is a left?handed helical network of hydrogen?bonds between the BTA cores surrounded by two right?handed helices of azobenzenes, which is experimentally recovered after depolymerisation. The responsiveness to two orthogonal triggers across a broad concentration range holds promise for use in e.g. photo?responsive gelation.