Abstract
Pathway complexity results in unique materials from the same components according to the assembly conditions. Here a chiral acyl-semicarbazide gelator forms three different gels of contrasting fibre morphology (termed ‘gelmorphs’) as well as lyotropic liquid crystalline droplets depending on the assembly pathway. The gels have morphologies that are either hyperhelical (HH-Gel), tape-fibre (TF-Gel) or thin fibril derived from the liquid crystalline phase (LC-Gels) and exhibit very different rheological properties. The gelator exists as three slowly interconverting conformers in solution. All three gels are comprised of an unsymmetrical, intramolecular hydrogen bonded conformer. The kinetics show that formation of the remarkable HH-Gel is cooperative and is postulated to involve association of the growing fibril with a non-gelling conformer. This single molecule dynamic conformational library shows how very different materials with different morphology and hence very contrasting materials properties can arise from pathway complexity as a result of emergent interactions during the assembly process.
| Original language | English |
|---|---|
| Pages (from-to) | 11389-11401 |
| Number of pages | 13 |
| Journal | Chemical Science |
| Volume | 14 |
| Issue number | 41 |
| DOIs | |
| State | Published - Sep 26 2023 |
Funding
We thank the Engineering and Physical Sciences Research Council for funding (EP/S035877/1), the Diamond Light Source for an award of instrument time on the Station I-19 (CY22240), and Dr Beth Bromley for access to the CD instrumentation. This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.