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In this work, we expound upon the manifestation of two supramolecular polymer polymorphs formed from a large discotic supramolecular monomer (rosette), which consists of six hydrogen-bonded molecules with an extended π-conjugated core. These polymorphs are generated in mixtures of chloroform and methylcyclohexane, attributable to distinctly differ-ent disc stacking arrangements. These arrangements can be classified as H-type and J-type stacking predicated on their distinctive photophysical properties. The H-type stacking, delineated by minimal rosette displacement, results in a twisted helix structure. Conversely, the J-type stacking, characterized by significant rosette displacement, induces inherent curvature in the supramolecular fiber, thereby culminating in a hollow helical coil (helicoid). While both polymorphs exhibit bistability in nonpolar solvent compositions, the H-type stacking attains stability purely in a kinetic sense within a polar solvent composition and undergoes conversion into the J-type stacking through a dislocation of stacked rosettes. This occurs without the dissociation and nucleation of monomers, leading to an unprece-dented helicoidal folding of supramolecular polymers. The direct helicoidal folding of supramolecular polymer fibers enables the trans-formation of extraordinarily long twisted helices into helicoids over the mesoscopic regime. Concurrently, distinct cohesive behaviors manifest in conjunction with the structural conversion observed within these extended supramolecular polymer materials. their ag-glomeration behaviors. Our findings not only augment our understanding of supramolecular polymer polymorphism, but they also highlight a distinctive method for achieving helicoidal folding in supramolecular polymers.

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• In Copyright
  

Keyword: Supramolecular chemistry, Atomic force microscopy, Transmission electron microscopy, Polymorphism

Date published: 2023-10-18

Publisher: American Chemical Society (ACS)

Journal:

• Journal of the American Chemical Society (ISSN: 00027863) vol. 145 issue. 41 p. 22563-22576

Funding:

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.4440

First published URL: https://doi.org/10.1021/jacs.3c07556

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Updated at: 2024-10-05 08:30:15 +0900

Published on MDR: 2024-10-05 08:30:15 +0900