POS2-1617
From Helices to Superhelices through Hierarchical Assembly across Competing Pathways
Topic
S2. High-End Characterization/Polymer Physics/Properties
When and Where
Sep 30, 2026
08:30 - 09:30
Room 301 (Grand Ballroom)
Session Chairs
Hae Jung SON
Boseok KANG
Presenter(s)
KYEONGIM HONG (ICMM-CSIC)
Co-Author(s)
Abstract
Understanding how molecular chirality propagates through competing self-assembly pathways to generate hierarchical structures remains a central challenge in supramolecular chemistry. Here we report a chiral π-conjugated quinquethiophene–rhodanine derivative that forms four distinct and isolatable supramolecular aggregates from a single enantiopure monomer under identical chemical conditions. These assemblies exhibit different chiroptical signatures, morphologies, and hierarchical organization, and can be selectively accessed through variations in thermal and mechanical treatment.
Calorimetric measurements enable the experimental construction of a supramolecular energy landscape that orders the aggregates according to their assembly enthalpy. Long-term kinetic studies and spectral deconvolution reveal mechanistic relationships between the structures, including the identification of an off-pathway hierarchical state and interconversions between helical assemblies. Most importantly, we show that the formation of the most stable structure proceeds through a helix-to-superhelix transition governed by concentration-dependent secondary nucleation. Together, these results provide a rare experimentally resolved example in which multiple supramolecular structures, their thermodynamic ordering, and their kinetic connectivity can all be established within a single molecular system, showing how pathway selection alone can program chirality, hierarchy, and morphology in supramolecular materials.
Calorimetric measurements enable the experimental construction of a supramolecular energy landscape that orders the aggregates according to their assembly enthalpy. Long-term kinetic studies and spectral deconvolution reveal mechanistic relationships between the structures, including the identification of an off-pathway hierarchical state and interconversions between helical assemblies. Most importantly, we show that the formation of the most stable structure proceeds through a helix-to-superhelix transition governed by concentration-dependent secondary nucleation. Together, these results provide a rare experimentally resolved example in which multiple supramolecular structures, their thermodynamic ordering, and their kinetic connectivity can all be established within a single molecular system, showing how pathway selection alone can program chirality, hierarchy, and morphology in supramolecular materials.
