|Title||Steering the Self-Assembly Outcome of a Single NDI Monomer into Three Morphologically Distinct Supramolecular Assemblies, with Concomitant Change in Supramolecular Polymerization Mechanism|
|Author(s)||Markiewicz, Grzegorz; Smulders, Maarten M.J.; Stefankiewicz, Artur R.|
|Source||Advanced Science 6 (2019)16. - ISSN 2198-3844|
|Publication type||Refereed Article in a scientific journal|
|Keyword(s)||naphthalene diimides - noncovalent self-assembly - nonequilibrium assemblies - self-assembly mechanism - supramolecular polymers|
Noncovalent self-assembly creates an effective route to highly sophisticated supramolecular polymers with tunable properties. However, the outcome of this assembly process is highly dependent on external conditions. In this work, a monomeric naphthalene diimide (NDI), designed to allow solubility in a wide range of solvents, can assemble into three distinct noncovalent supramolecular species depending on solvent composition and temperature. Namely, while the self-assembly in chlorinated solvents yields relatively short, hydrogen-bonded nanotubes, the reduction of solvent polarity changes the assembly outcome, yielding π–π stacking polymers, which can further bundle into a more complex aggregate. The obtained polymers differ not only in their global morphology but—more strikingly—also in the thermodynamics and kinetics of their supramolecular self-assembly, involving isodesmic or two-stage cooperative assembly with kinetic hysteresis, respectively. Ultimately, three distinct assembly states can be accessed in a single experiment.