To Fold or to Assemble?

We introduce a new class of foldable oligomers consisting of alternating rigid and flexible regions. The rigid segments overlap to give pi-stacked folded conformers whose formation is driven mostly by pi-pi molecular orbital overlaps. As the oligomer concentration increases, the folded molecular structures further self-assemble into larger nanostructures. The dynamic processes of folding and self-organization are monitored with absorption, fluorescence, and NMR spectroscopies. Our results show that folding dominates at low concentrations (< approximately 1 mM) and precedes self-assembly, which occurs over the initial concentration range of approximately 1-100 mM.