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Title: | Nonclassical Crystal Growth of Supramolecular Polymers in Aqueous Medium |
Authors: | Elizebath, D Lim, J H Nishiyama, Y Vedhanarayanan, B Saeki, A Ogawa, Y Praveen, V K |
Issue Date: | Feb-2024 |
Publisher: | Wiley Online Library |
Citation: | Small; 20(6):2306175 |
Abstract: | A mechanistic understanding of the principles governing the hierarchical organization of supramolecular polymers offers a paradigm for tailoring synthetic molecular architectures at the nano to micrometric scales. Herein, the unconventional crystal growth mechanism of a supramolecular polymer of superbenzene(coronene)-diphenylalanine conjugate (Cr-FFOEt) is demonstrated. 3D electron diffraction (3D ED), a technique underexplored in supramolecular chemistry, is effectively utilized to gain a molecular-level understanding of the gradual growth of the initially formed poorly crystalline hairy, fibril-like supramolecular polymers into the ribbon-like crystallites. The further evolution of these nanosized flat ribbons into microcrystals by oriented attachment and lateral fusion is probed by time-resolved microscopy and electron diffraction. The gradual morphological and structural changes reveal the nonclassical crystal growth pathway, where the balance of strong and weak intermolecular interactions led to a structure beyond the nanoscale. The role of distinct π-stacking and H-bonding interactions that drive the nonclassical crystallization process of Cr-FFOEt supramolecular polymers is analyzed in comparison to analogous molecules, Py-FFOEt and Cr-FF forming helical and twisted fibers, respectively. Furthermore, the Cr-FFOEt crystals formed through nonclassical crystallization are found to improve the functional properties. |
URI: | https://onlinelibrary.wiley.com/doi/10.1002/smll.202306175 http://localhost:8080/xmlui/handle/123456789/4920 |
Appears in Collections: | 2024 |
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File | Description | Size | Format | |
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Nonclassical Crystal Growth of Supramolecular Polymers in Aqueous Medium_ElizebathD_Small.pdf Restricted Access | 2.86 MB | Adobe PDF | View/Open Request a copy |
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