The structural and dynamical properties of dilute aqueous solutions of poly(ethylene glycol)–perylene diimides (PEGn–PDI) have been investigated by means of static and dynamic light scattering, TEM microscopy, and small-angle X-ray scattering experiments. The amphiphilic PEGn–PDI molecules first self-assemble into stable and compact primary stacks of a few units of planar PDI through hydrophobic and π–π interactions. These primary stacks subsequently arrange in large and globular aggregates of typically 100–250 nm via weak PEG chain interpenetration. Surprisingly, the scattered electric field autocorrelation function g(1)(q,t) measured by dynamic light scattering evolves over very long periods of times (several months) and up to a bimodal distribution. The fast relaxation mechanism is associated to the diffusion of free primary stacks, whereas the slower relaxation still indicates the presence of large self-assemblies. Kinetic experiments show that the large supramolecular aggregates slowly release the free primary stacks whose proportion increases with time. This dissociation depends on several parameters such as PEG side chain length, total concentration, and shaking.
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