Computational Methods Elucidate the role of Water in a Supramolecular Polymerization in Oils

Mathijs Mabesoone m.f.j.mabesoone@tue.nl ¹ Nathan van Zee ¹ Beatrice Adelizzi ¹ Ivo Filot ^1,2 Anja Palmans ¹ E.W. Meijer ¹

¹Eindhoven University of Technology, Institute for Complex Molecular Systems, Eindhoven, The Netherlands
²Eindhoven University of Technology, Inorganic Materials Chemistry, Eindhoven, The Netherlands

The interactions of water are of great importance in the structure of self-assembled structures, including proteins¹ and synthetic molecules.² Nevertheless, fundamental mechanisms of the way water directs these self-assembled structures are largely unknown. Here, we show that the morphology of a biphenyl derived supramolecular polymer is dictated by small amounts of water present in methylcyclohexane (MCH) solutions.³ With the use of theoretical considerations in combination with a numerical thermodynamic model insight is gained in the mechanism of the water-dependent polymerization and a full thermodynamic characteristics of this water-regulated polymerization is obtained. We show that the competition of multiple pathways in supramolecular polymerizations gives rise to systems that are extremely sensitive to temperature, whereas a change in temperature does not result in a different behavior of the polymers. The implications of water in supramolecular polymerizations is not limited to a small number of molecules, but appears to be more general, as is shown with several examples.

References

Science 336, 320-323 (2012)
J. Am. Chem. Soc. 129, 5735-5743 (2007)
Science 265, 936-937 (1994).