Effect of Core Oligomer Length on the Phase Behavior and Assembly of π-Conjugated Peptides

Biohybrid molecules are a versatile class of materials for controlling the assembly behavior and functional properties of electronically active organics. In this work, we study the effect of the size of the π-conjugated core on the assembly and phase behavior for a series of π-conjugated peptides consisting of oligothiophene cores of defined lengths flanked by sequence-defined peptides (OTX, where X = 4, 5, 6 is the number of thiophene core units). Interestingly, we find that π-conjugated peptides with relatively short OT4 cores assemble into ordered, high aspect ratio, one-dimensional (1D) structures, whereas π-conjugated peptides with longer OT5 and OT6 cores assemble into disordered structures or lower aspect ratio 1D structures depending on assembly conditions. Phase diagrams for assembled materials are experimentally determined as a function of ionic strength, pH, temperature, and peptide concentration, revealing the impact of molecular sequence and π-conjugated core length on assembled morphologies. Molecular dynamics (MD) simulations are further used to probe the origins of microscale differences in assembly that arise from subtle changes in molecular identity. Broadly, our work elucidates the mechanisms governing the assembly of π-conjugated peptides, which will aid in efficient materials processing for soft electronic applications. Overall, these results highlight the complex phase behavior of biohybrid materials, including the impact of molecular sequence on assembly behavior and morphology.