Modulating Orientational Order to Organize Polyhedral Nanoparticles into Plastic Crystals and Uniform Metacrystals

In nanoparticle self‐assembly, the current lack of strategy to modulate orientational order creates challenges in isolating large‐area plastic crystals. Here, we achieve two orientationally distinct supercrystals using one nanoparticle shape, including plastic crystals and uniform metacrystals. Our...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2020-11, Vol.59 (47), p.21183-21189
Main Authors: Lee, Yih Hong, Shi, Wenxiong, Yang, Yijie, Kao, Ya‐Chuan, Lee, Hiang Kwee, Chu, Rongrong, Pang, Yee Ling, Lay, Chee Leng, Li, Shuzhou, Ling, Xing Yi
Format: Article
Language:English
Subjects:
Assembly
Chains (polymeric)
Configurations
Crystal structure
Crystals
Molecular chains
nanoparticle self-assembly
Nanoparticles
nanoscale surface chemistry
orientational order
plastic crystals
Plastics
Polyhedra
Polymers
uniform metacrystals
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Summary:In nanoparticle self‐assembly, the current lack of strategy to modulate orientational order creates challenges in isolating large‐area plastic crystals. Here, we achieve two orientationally distinct supercrystals using one nanoparticle shape, including plastic crystals and uniform metacrystals. Our approach integrates multi‐faceted Archimedean polyhedra with molecular‐level surface polymeric interactions to tune nanoparticle orientational order during self‐assembly. Experiments and simulations show that coiled surface polymer chains limit interparticle interactions, creating various geometrical configurations among Archimedean polyhedra to form plastic crystals. In contrast, brush‐like polymer chains enable molecular interdigitation between neighboring particles, favoring consistent particle configurations and result in uniform metacrystals. Our strategy enhances supercrystal diversity for polyhedra comprising multiple nondegenerate facets. Gaining control over the orientational order of nanoparticles, and by extension the formation of plastic crystals over large areas, remains challenging. Molecular‐level polymeric surface interactions are now employed to modulate the orientational order of Archimedean nanoparticles. Two orientationally distinct supercrystals are formed using a single nanoparticle shape, including plastic crystals and uniform metacrystals.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202009941