Extraordinary Acceleration of Cogwheel Helical Self-Organization of Dendronized Perylene Bisimides by the Dendron Sequence Encoding Their Tertiary Structure.

The cogwheel model of hierarchical self-organization provides a route to highly ordered crystalline helical columnar hexagonal arrays of perylene bisimides (PBIs) conjugated to (3,4,5)-dimethyloctyl (racemic dm8*, r) minidendrons. Cogwheel PBIs assemble with identical structural order irrespective of molecular chirality to generate helical columns jacketed with an alkyl coat with length equal to half the helical pitch, exhibiting helical deracemization in the crystal state. These assemblies were accessible only via annealing or cooling and reheating at 1 °C/min. Recently it was discovered that hybrid rr8 sequence-defined dendrons with r and linear n-octyl (8) chains enabled the formation of the cogwheel phase at 10 °C/min upon heating but not cooling. Here we report four libraries of hybrid PBIs with sequence-defined dendrons containing r and n-alkyl (CnH2n+1) chains with n = 6, 7, 9, and 10. Structural analysis of these libraries by fiber X-ray diffraction and differential scanning calorimetry reveals that the 9r9 sequence enables an extraordinary acceleration of cogwheel assembly at rates of up to 50 °C/min on heating and cooling, providing, to the best of our knowledge, the fastest crystallizing supramolecular or covalent macromolecule known. Solid-state NMR studies help to elucidate this unexpected and unprecedented extraordinary acceleration of hierarchical self-organization, which arises from a combination of crystal packing of the ideal tertiary structure and alkyl chain dynamics. This general model raises questions about the use of achiral motifs to achieve high structural order in chiral systems and the need for disorder to create order in complex biological and bioinspired synthetic systems.