Pathway complexity in supramolecular polymerization

Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process...

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Bibliographic Details
Published in:	Nature (London) 2012-01, Vol.481 (7382), p.492-496
Main Authors:	KOREVAAR, Peter A, GEORGE, Subi J, MARKVOORT, Albert J, SMULDERS, Maarten M. J, HILBERS, Peter A. J, SCHEMING, Albert P. H. J, DE GREEF, Tom F. A, MEIJER, E. W
Format:	Article
Language:	eng
Subjects:	Agglomeration Applied sciences Assembly Binding, Competitive Circular Dichroism Exact sciences and technology Experiments Helicity Kinetics Models, Molecular Organic polymers Organizations Pathways Physicochemistry of polymers Polymerization Polymers - chemistry Properties and characterization Proteins - chemistry Self assembly Solution and gel properties Spectrum analysis Studies Supramolecular polymers Tartaric acid Tartrates - chemistry Thermodynamics
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Summary:	Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. In the case of protein fibrils, formation and growth have been attributed to complex aggregation pathways that go beyond traditional concepts of homogeneous and secondary nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated, but our quantitative understanding of the processes involved remains limited. Here we report time-resolved observations of the formation of supramolecular polymers from π-conjugated oligomers. Our kinetic experiments show the presence of a kinetically favoured metastable assembly that forms quickly but then transforms into the thermodynamically favoured form. Quantitative insight into the kinetic experiments was obtained from kinetic model calculations, which revealed two parallel and competing pathways leading to assemblies with opposite helicity. These insights prompt us to use a chiral tartaric acid as an auxiliary to change the thermodynamic preference of the assembly process. We find that we can force aggregation completely down the kinetically favoured pathway so that, on removal of the auxiliary, we obtain only metastable assemblies.
ISSN:	0028-0836 1476-4687