超分子化学
堆积
结晶
超分子聚合物
材料科学
结晶学
聚合物
分子间力
晶体工程
微晶
晶体生长
分子
纳米技术
晶体结构
化学
有机化学
复合材料
作者
Drishya Elizebath,Jia Hui Lim,Yoshiharu Nishiyama,Balaraman Vedhanarayanan,Akinori Saeki,Yu Ogawa,Vakayil K. Praveen
出处
期刊:Small
[Wiley]
日期:2023-09-28
卷期号:20 (6)
被引量:8
标识
DOI:10.1002/smll.202306175
摘要
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‐FF OEt ) 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‐FF OEt supramolecular polymers is analyzed in comparison to analogous molecules, Py‐FF OEt and Cr‐FF forming helical and twisted fibers, respectively. Furthermore, the Cr‐FF OEt crystals formed through nonclassical crystallization are found to improve the functional properties.
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