Deciphering Temperature-Driven Pathway Complexity in Supramolecular Self-Assembly: Impact on Chiroptical, Nanostructural, and Electrical Behavior

Controlling supramolecular self-assembly and the resulting nanostructures is crucial for tailoring the functional properties of supramolecular materials. Their stimuli-responsive nature and ability to access multiple energy minima through pathway complexity enable dynamic structural transformations with distinct material outcomes. This approach is highly attractive for its precise control over a wide range of nanostructures and for enabling a detailed mechanistic analysis through various spectroscopic and microscopic techniques. In this work, we report a temperature-modulated investigation of the supramolecular self-assembly of a naphthalenediimide-based chiral amphiphile. The system exhibited pathway complexity, leading to the formation of chiroptically active nanodisks as kinetically controlled products. Upon thermal treatment, a nanostructural transition was observed, yielding 2D nanosheets as the thermodynamically stable state, driven by reorganization of π–π-stacking interactions. Along with these morphological transformations, we observed a remarkable change in macroscopic chirality, where the supramolecular chirality progressively diminished as the system transitioned from the kinetic to the thermodynamic state. To evaluate the implications of these transformations, we measured the electrical conductivity, which reflects the influence of the nanostructure, molecular packing, and chiroptical behavior on the the overall material performance. This study highlights the potential of these supramolecular assemblies, demonstrating that their molecular orientation strongly influences the macroscopic properties and gives rise to intriguing behavior. Such fundamental insights provide a guiding framework for the rational design of tunable materials with future relevance in optoelectronic, bioelectronic, and sensing devices.