Unveiling One-Dimensional Supramolecular Structures Formed through π-π Stacking of Phenothiazines by Differential Pulse Voltammetry

Abstract Organic‐based nanomaterials can be self‐assembled by strong and directional intermolecular forces such as π–π interactions. Experimental information about the stability, size, and geometry of the formed structures is very limited for species that easily aggregate, even at very low concentrations. Differential pulse voltammetry (DPV) can unveil the formation, growth, and also the stability window of ordered, one‐dimensional, lamellar self‐aggregates formed by supramolecular π stacking of phenothiazines at micromolar (10 −6 mol L −1 ) concentrations. The self‐diffusion features of the species at different concentrations are determined by DPV and used to probe the π staking process through the concept of the frictional resistance. It is observed that toluidine blue and methylene blue start to self‐aggregate around 9 μmol L −1 , and that the self‐aggregation process occurs by one‐dimensional growth as the concentration of the phenothiazines is increased up to around 170 μmol L −1 for toluidine blue and 200 μmol L −1 for methylene blue. At higher concentrations, the aggregation process leads to structures with lower anisometry.