Probing the solvent-assisted nucleation pathway in chemical self-assembly.
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.
Jonkheijm
Pascal
P
Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, Post Office Box 513, 5600 MB Eindhoven, Netherlands.
van der Schoot
Paul
P
Schenning
Albertus P H J
AP
Meijer
E W
EW