The influence of substituents on gelation and stacking order of oligoaramid – based supramolecular networks

Self-assembly has proven to be a powerful tool for functional, smart materials such as hydrogels derived from low molecular weight compounds. However, the targeted design of functional gelators remains difficult. Here, we present a set of four Y-shaped aromatic amide tetramers with varying functionalities able to undergo different non- covalent interactions. These compounds were explored towards their self-assembly behavior and hydrogel formation by experimental methods such as UV-vis spectroscopy, rheology, small angle X-ray scattering (SAXS), scanning/transmission electron, and atomic force microscopy. Additionally, we investigated the main mechanisms behind oligomer aggregation and the structure of the resulting supramolecular chains through full atomistic molecular dynamics simulations.