Science · 2006 · 918 citations · 17 references
Natural SciencesChemistryMolecular BiophysicsNanomaterialsSupramolecular ChemistryMacromolecular AssemblyMacromolecular StructureNucleationSelf-assembled NanostructuresSelf-assemblySupramolecular GelsConjugated MoleculesHierarchical Self-assemblyMolecular Self-assemblyNanostructuresOrdered NanostructuresSelf-assembly ThermodynamicsSolvent StructureSupramolecular Self-assembly
Hierarchical self‑assembly is a powerful strategy for creating molecular nanostructures, yet its mechanistic details remain poorly understood. The authors spectroscopically monitored nucleation of p‑conjugated molecules into helical fibrillar structures and showed that an organized solvent shell rigidifies aggregates and directs further bundle or gel assembly. The data reveal a nucleation‑growth pathway with high cooperativity and a helical transition in the nucleating species, driven by solvent‑mediated aggregation.
Hierarchical self-assembly offers a powerful strategy for producing molecular nanostructures. Although widely used, the mechanistic details of self-assembly processes are poorly understood. We spectroscopically monitored a nucleation process in the self-assembly of p-conjugated molecules into helical supramolecular fibrillar structures. The data support a nucleation-growth pathway that gives rise to a remarkably high degree of cooperativity. Furthermore, we characterize a helical transition in the nucleating species before growth. The self-assembly process depends strongly on solvent structure, suggesting that an organized shell of solvent molecules plays an explicit role in rigidifying the aggregates and guiding them toward further assembly into bundles and/or gels.
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