The performance of self-assembled systems in functional organic materials with electronic or bioactive properties critically depends on the organization and dynamics of the molecular building blocks. Understanding the self-assembly pathways involved in the formation of these supramolecular materials is essential. Although studies under thermodynamic and kinetic control have been performed, quantitative insight into the self-assembly pathways of these structures is lacking. Recent studies on the growth of protein fibrils introduced the concept of pathway complexity extending the traditional concepts of homogeneous and secondary nucleation events in single pathway assemblies. We will discuss crucial steps in the quantitative understanding of pathway complexity in synthetic homogeneous supramolecular polymerizations using chirality as an experimental tool. By obtaining these kinetic parameters, it is now possible to disclose hidden pathways during supramolecular polymerization processes. In the presentation, we show that the chemical self-assembly of chiral π-conjugated oligomers, operates via a nucleation – elongation pathway and hence is highly cooperative. As a result the solvent plays an essential role in the chemical self-assembly and strong evidence is found that the alkane solvents are co-organized with the oligomeric stack. These results are also of crucial importance for the discussion whether the chemical self-assembly creates the thermodynamically determined product or that is possible to form kinetically trapped structures as well. With this knowledge we will show some new functional supramolecular materials.
