Probing the Solvent-Assisted Nucleation Pathway in Chemical Self-Assembly
Pascal Jonkheijm,1*
Paul van der Schoot,2
Albertus P. H. J. Schenning,1
E. W. Meijer1
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.
2 Polymer Physics Group, Eindhoven University of Technology, Post Office Box 513, 5600 MB Eindhoven, Netherlands.
* Present address: Chemical Biology, Max Planck Institute for Molecular Physiology, Otto Hahnstrasse 11, 44227 Dortmund, Germany.
To whom correspondence should be addressed. E-mail: e.w.meijer{at}tue.nl (E.W.M.); a.p.h.j.schenning{at}tue.nl (A.P.H.J.S.)
