Tuning Optoelectronic and Chiroptic Properties of Peptide-Based Materials by Controlling the Pathway Complexity.

Supramolecular chemistry has evolved from the traditional focus on thermodynamic on-pathways to the complex study of kinetic off-pathways, which are strongly dependent on environmental conditions. Moreover, the control over pathway complexity allows nanostructures to be obtained that are inaccessible through spontaneous thermodynamic processes. Herein, we present a family of peptide-based π-extended tetrathiafulvalene (exTTF) molecules that show two self-assembly pathways leading to two distinct J-aggregates, namely metastable (M) and thermodynamic (T), with different spectroscopic, chiroptical, and electrochemical behavior. Moreover, cryo-transmission electron microscopy (cryo-TEM) reveals a different morphology for both aggregates and a direct observation of the morphological transformations from tapes to twisted ribbons.