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. Take the complex path! Comprehensive study of polymerization pathways of minimalistic peptide molecules and the direct impact of these pathways on morphology and electrochemical properties (see figure).