Unraveling the Supramolecular Organization Mechanism of Chiral Star-Shaped Poly(3-alkylthiophene)

The supramolecular organization of star-shaped polythiophenes was investigated in a solvent/nonsolvent system and upon cooling. Both systems yield entirely different supramolecular aggregates. Classical characterization techniques can give some insight; the exact mechanism is currently not understood. By introducing second- and third-harmonic light scattering and its combination with other optical techniques, we were able to fully investigate the evolution of the supramolecular organization in both regimes. This approach allowed an unprecedented insight into the different stages of the process. A markedly different assembly mechanism is proposed for both regimes, which results in a different supramolecular organization of the polymer.