Effect of Spacer Length and Solvent on the Concentration-Driven Aggregation of Cationic Hydrogen-Bonding Donor Polythiophenes

[Image: see text] Aggregation of cationic isothiouronium polythiophenes with alkoxy-spacers of different lengths at the 3-position of the thiophene ring was studied in solvents of different polarities. Hydrogen-bonding capacity was assessed by steady-state absorption and fluorescence spectroscopy, whereas the aggregation in aqueous solutions was studied by electron paramagnetic resonance spectroscopy, using paramagnetic probes of different polarities. The two polymers displayed similar features in respect to conformation, effect of cosolvents on aggregation, unstructured absorption–fluorescence spectra, Stokes shifts when aggregated, solvatochromic effect, and self-quenching concentration. However, these polymers also showed different specific interactions with water, Stokes shifts in water, effect of the solvent on the extent of dominant state of the S1 level, and also different inner cavities and hydrophobic–hydrophilic surface area in aqueous solution aggregates. Water maximized the difference between the polymers concerning the effect of specific increases in concentration, whereas the presence of 1,4-dioxane generated almost identical effects on both polymers.