Scheme 1.

a) Hierarchical self‐assembly through intermolecular H‐bonding and hydrophobic interactions of diacetylene bisurea bolaamphiphiles followed by topochemical polymerization of the stacked diacetylenes. Aggregation of 9–10 ribbons into semi‐flexible fibres followed by covalent crosslinking into strain‐stiffening networks. b) Photo‐polymerization of the assembled diacetylene groups (i.e. covalent fixation) and the resulting PDAs. c) Gel preparation method involving separate co‐assembly and covalent fixation of DA‐Ac and DA‐N3 analogues with DA followed by mixing and gelation through CuAAC cycloaddtion reaction.