Self-sorting and co-assembly control in multicomponent supramolecular hydrogels with dual monomer and polymer statistical distribution

Multicomponent supramolecular polymer gels are a class of soft matter materials which form via the assembly of two or more small molecules. Different structures can be generated with interesting potential functions and applications. Insight into the assembly mechanism is key in the design of these systems for specific applications. Herein, a series of hydrogels with diverse structures and functionalities were synthesised. Using dynamic covalent chemistry as a key tool we show that it is possible to control the monomer assembly, forming both self-sorted and co-assembled polymers and gels from the same initial components. The hierarchical structure of the gels is difficult to elucidate. We emphasise the significance of small-angle neutron scattering (SANS) and spin-echo SANS (SESANS) measurements in characterising these intricate assemblies and demonstrate that these techniques are able to differentiate among self-sorted and co-assembled structures even when using chemically similar components.