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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 blocks1,2,3,4,5. 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 pathways6,7,8 that go beyond traditional concepts of homogeneous9,10,11 and secondary12,13,14 nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated15,16,17,18, 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 process19. 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.

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Figure 1: Pathway complexity in supramolecular polymerization of SOPV.
Figure 2: Experiments under kinetic control.
Figure 3: Analysis aggregation pathway competition with kinetic model.
Figure 4: Controlled formation of exclusively metastable aggregates via a two-step non-covalent synthetic methodology.


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We thank Ž. Tomović for providing the SOPV. We are grateful to R. M. Kellogg (Syncom, Groningen, The Netherlands) for providing the tartaric acid derivate. We also thank H. W. H. van Roekel and R. de Bruijn for discussions. Artwork was provided by K. Pieterse. The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013)/ERC grant agreement number 246829, and from the Netherlands Organization for Scientific Research.

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Authors and Affiliations



P.A.K. and M.M.J.S. performed the stopped-flow experiments. P.A.K., A.J.M. and T.F.A.D.G. analysed the data and developed the kinetic model. S.J.G. performed the experiments with DTA and SOPV. E.W.M., T.F.A.D.G., A.P.H.J.S. and P.A.J.H. supervised the research. P.A.K., T.F.A.D.G. and E.W.M. wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Tom F. A. De Greef or E. W. Meijer.

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The authors declare no competing financial interests.

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Korevaar, P., George, S., Markvoort, A. et al. Pathway complexity in supramolecular polymerization. Nature 481, 492–496 (2012).

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