Shape Matching in Superatom Chemistry and Assembly
- Jingjing YangJingjing YangDepartment of Chemistry, Columbia University, New York, New York 10027, United StatesMore by Jingjing Yang
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- Feifan WangFeifan WangDepartment of Chemistry, Columbia University, New York, New York 10027, United StatesMore by Feifan Wang
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- Jake C. RussellJake C. RussellDepartment of Chemistry, Columbia University, New York, New York 10027, United StatesMore by Jake C. Russell
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- Taylor J. HochuliTaylor J. HochuliDepartment of Chemistry, Columbia University, New York, New York 10027, United StatesMore by Taylor J. Hochuli
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- Xavier RoyXavier RoyDepartment of Chemistry, Columbia University, New York, New York 10027, United StatesMore by Xavier Roy
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- Michael L. SteigerwaldMichael L. SteigerwaldDepartment of Chemistry, Columbia University, New York, New York 10027, United StatesMore by Michael L. Steigerwald
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- Xiaoyang ZhuXiaoyang ZhuDepartment of Chemistry, Columbia University, New York, New York 10027, United StatesMore by Xiaoyang Zhu
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- Daniel W. Paley*Daniel W. Paley*[email protected]Columbia Nano Initiative, Columbia University, New York, New York 10027, United StatesMore by Daniel W. Paley
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- Colin Nuckolls*Colin Nuckolls*[email protected]Department of Chemistry, Columbia University, New York, New York 10027, United StatesMore by Colin Nuckolls
Abstract
Creating structures with superatomic nanoclusters rather than atoms offers the possibility of new hierarchical solids with collective properties. The variability of chemical compositions, sizes, and shapes of these superatomic building blocks provides great opportunities to access unknown assemblies. Herein we explore this concept by using geometrically anisotropic superatomic nanoclusters as building blocks. We reveal a series of novel superatomic architectures that are built from rod-shaped Co12Se16(PEt3)10 and C140 nanoclusters. More importantly, these assemblies show nonclose packings that afford voids to accommodate solvent molecules as a result of the shape anisotropy of the constituent building blocks. These intercalated small molecules act as “crystal modulators” to modulate the solid-state structures and properties. As a result, we are able to tune the crystal packings and optical gaps of the solids and see the moment when electrical conduction is “turned on”. Our results demonstrate the vast potential of using anisotropic superatomic nanoclusters to create solid-state materials and provide a novel approach to configure their assemblies and properties.
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(34)
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(11)
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(1)
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(3)
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(1)
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(6)
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(29)
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(9)
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6
Se
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2. Nanoscale 2021, 13
(37)
, 15763-15769. https://doi.org/10.1039/D1NR00876E
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(12)
https://doi.org/10.1063/5.0062582