Polymer deaggregation and assembly controlled by a double cavity cucurbituril

A supramolecular polymer was prepared from a mixture of poly(diallyldimethylammonium chloride) (1) and bis-ns-CB[10]. The repeat units of the polymer chain are capable of binding inside each of the two cavity domains of bis-ns-CB[10]. The bis-ns-CB[10] molecular containers complex the sides of the polymer chain - which we term a cupping interaction - thereby promoting the association of individual polymer strands to form 1n root bis-ns-CB[10]m, which results in an extension of the length of the polymer. The effect of bis-ns-CB[10] on the physical properties of the polymer was investigated using viscometry in dilute aqueous solution. A decrease in rel was observed upon increasing the concentrations of bis-ns-CB[10] to a solution of 1. Atomic force microscopy and diffusion-ordered spectroscopy were performed to probe the mode of interaction between polymer 1 and bis-ns-CB[10]. Collectively, the data support the two roles for bis-ns-CB[10]: (1) as a deaggregation agent at lower concentrations and (2) as a cupping agent that non-covalently links individual polymer strands at higher concentrations resulting in overall extension of the polymer.