Thiosquaramide-Based Supramolecular Polymers: Aromaticity Gain in a Switched Mode of Self-Assembly
Journal of the American Chemical Society, vol. 142, pp. 19907–19916
Abstract
Despite a growing understanding of factors that drive monomer self-assembly to form supramolecular polymers, the effects of aromaticity gain have been largely ignored. Herein, we document the aromaticity gain in two different self-assembly modes of squaramide-based bolaamphiphiles. Importantly, O → S substitution in squaramide synthons resulted in supramolecular polymers with increased fiber flexibility and lower degrees of polymerization. Computations and spectroscopic experiments suggest that the oxo- and thiosquaramide bolaamphiphiles self-assemble into "head-to-tail" versus "stacked" arrangements, respectively. Computed energetic and magnetic criteria of aromaticity reveal that both modes of self-assembly increase the aromatic character of the squaramide synthons, giving rise to stronger intermolecular interactions in the resultant supramolecular polymer structures. These examples suggest that both hydrogen-bonding and stacking interactions can result in increased aromaticity upon self-assembly, highlighting its relevance in monomer design.
Authors 13
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Affiliation as printed
Leiden University , , P.O. Box 9502, , ,
Supramolecular and Biomaterials Chemistry, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA, Leiden, The Netherlands
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Affiliation as printed
Leiden University , , P.O. Box 9502, , ,
Supramolecular and Biomaterials Chemistry, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA, Leiden, The Netherlands
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Affiliation as printed
University of Houston , , , ,
Department of Chemistry, University of Houston, Houston, Texas 77204, United States
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Affiliation as printed
University of Houston , , , ,
Department of Chemistry, University of Houston, Houston, Texas 77204, United States
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Affiliation as printed
Leiden University , , P.O. Box 9502, , ,
Supramolecular and Biomaterials Chemistry, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA, Leiden, The Netherlands
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Affiliation as printed
Leiden University , , P.O. Box 9502, , ,
Supramolecular and Biomaterials Chemistry, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA, Leiden, The Netherlands
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Affiliation as printed
University of Houston , , , ,
Department of Chemistry, University of Houston, Houston, Texas 77204, United States
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Affiliation as printed
Leiden University , , P.O. Box 9502, , ,
Supramolecular and Biomaterials Chemistry, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA, Leiden, The Netherlands
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Norwegian University of Science and Technology
Affiliation as printed
Norwegian University of Science and Technology , , ,
Department of Chemistry, Norwegian University of Science and Technology, 7491 Trondheim, Norway
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Delft University of Technology
Affiliation as printed
Delft University of Technology , , Leeghwaterstraat 39 , ,
Process & Energy Laboratory, Delft University of Technology, Leeghwaterstraat 39, 2628 CB Delft, The Netherlands
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Eindhoven University of Technology
Affiliation as printed
Eindhoven University of Technology , , P.O. Box 513, , ,
Laboratory of Self-Organizing Soft Matter and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MD, Eindhoven, The Netherlands
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Judy I-Chia Wu corresponding
Affiliation as printed
University of Houston , , , ,
Department of Chemistry, University of Houston, Houston, Texas 77204, United States
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Affiliation as printed
Leiden University , , P.O. Box 9502, , ,
Supramolecular and Biomaterials Chemistry, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA, Leiden, The Netherlands
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