Thiosquaramide-Based Supramolecular Polymers: Aromaticity Gain in a Switched Mode of Self-Assembly

Victorio Saez Talens, Joyal Davis, Chia Hua Wu, Zhili Wen, Francesca Lauria, Karthick Babu Sai Sankar Gupta, Raisa Rudge, Mahsa Boraghi, Alexander Hagemeijer, Thuat T. Trinh, Pablo Englebienne, Ilja K. Voets, Judy I. Wu (Corresponding author), Roxanne E. Kieltyka (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

23 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)19907-19916
Number of pages10
JournalJournal of the American Chemical Society
Volume142
Issue number47
DOIs
Publication statusPublished - 25 Nov 2020

Funding

We would like to thank T. Sharp, R. I. Koning, and B. Koster for assistance with cryo-TEM experiments; L. C. Gascoigne for SLS measurements; G. Fernández, K. Kartha, W. E. M. Noteborn, and A. Kros for fruitful discussions; and R. Das for computing the electron density difference maps. I.K.V. (NWO ECHO-STIP Grant 717.013.005, NWO VIDI Grant 723.014.006) and R.E.K. (NWO-ECHO-STIP Grant 717.014.005, NWO-VENI Grant 722.012.011) acknowledge The Netherlands Organization for Scientific Research (NWO) for funding. J.I.W. thanks the National Science Foundation (NSF) (CHE-1751370) and the National Institute of General Medical Sciences (NIGMS) of the National Institute of Health (R35GM133548) for grant support, as well as computational resources provided by the uHPC cluster, managed by the University of Houston and acquired through support from the NSF (MRI-1531814).

FundersFunder number
NWO-ECHO-STIP717.014.005
NWO‐VENI722.012.011
National Science FoundationCHE-1751370
National Institutes of Health
National Institute of General Medical SciencesR35GM133548
University of HoustonMRI-1531814
Nederlandse Organisatie voor Wetenschappelijk Onderzoek723.014.006, 717.013.005

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