Thiosquaramide-Based Supramolecular Polymers
Aromaticity Gain in a Switched Mode of Self-Assembly
Victorio Saez Talens (Universiteit Leiden)
Joyal Davis (Universiteit Leiden)
Chia Hua Wu (University of Houston)
Zhili Wen (University of Houston)
Francesca Lauria (Universiteit Leiden)
Karthick Babu Sai Sankar Gupta (Universiteit Leiden)
Raisa Rudge (Universiteit Leiden)
Mahsa Boraghi (University of Houston)
Alexander Hagemeijer (Universiteit Leiden)
Thuat T. Trinh (Norwegian University of Science and Technology (NTNU))
Pablo Englebienne (Lejeune Association Management)
Ilja K. Voets (Eindhoven University of Technology)
Judy I. Wu (University of Houston)
Roxanne E. Kieltyka (Universiteit Leiden)
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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.
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