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Influence of the Solvent and the Enantiomeric Purity on the Transition between Different Supramolecular Polymers

Authors

  • Dr. Martin Wolffs,

    1. Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
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  • Juliën L. J. van Velthoven,

    1. Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
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  • Dr. Xianwen Lou,

    1. Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
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  • Ralf A. A. Bovee,

    1. Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
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  • Maarten Pouderoijen,

    1. Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
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  • Joost L. J. van Dongen,

    1. Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
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  • Dr. Albertus P. H. J. Schenning,

    Corresponding author
    1. Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
    • Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
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  • Prof. Dr. E. W. Meijer

    Corresponding author
    1. Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
    • Institute for Complex Molecular Systems and the Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (The Netherlands), Fax: (+31) 40-2474706
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Abstract

The self-assembly of two enantiomerically pure hexa(oligo (p-phenylene vinylene))-substituted benzenes having 24 stereocenters was studied in pure methylcyclohexane (MCH) and in a mixture of MCH/toluene (4:1). Irrespective of the solvent a cooperative supramolecular polymerization mechanism was determined for these star-shaped molecules by using temperature-dependent CD and UV/Vis spectroscopy. Quite remarkably, a transition from one helical supramolecular state (A) to a second more thermodynamically stable supramolecular helical assembly (B) was observed. The rate of the A→B transition was strongly dependent on the nature of the solvent; being faster in the solvent mixture than in pure MCH. By using size exclusion chromatography we could relate the increased rate to a decreased stability of the supramolecular A state in the solvent mixture. Next, we mixed the two enantiomerically pure hexa-substituted benzene derivatives in a so-called majority-rules experiment, which lead to the anitcipated chiral amplification in the A state. More importantly it appeared that the A→B transition was significantly hampered in these mixed systems. Furthermore, the absence of chiral amplification in the B state revealed the formation of separated enantiomerically pure assemblies. Therefore, by using a wide variety of spectroscopic and chromatographic techniques we determined the influence of solvent and enantiomeric purity on the transition between different supramolecular states.

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