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Title: Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations

Abstract

Superatoms are nanometer-sized molecules or particles that form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in lattices of quantum dots, p-block clusters, and fullerenes. In this report, we introduce a family of uranium-oxysulfate cluster anions whose hierarchical assembly in water is controlled by two parameters: acidity and the lanthanide or transition-metal countercation. In acid, larger LnIII (Ln = La–Ho) link hexamer (U6) oxoclusters into body-centered cubic frameworks, while smaller LnIII (Ln = Er–Lu and Y) promote linking of 14 U6 clusters into hollow superclusters (U84 superatoms). U84 assembles into superlattices including cubic-closest packed, body-centered cubic, and interpenetrating networks, bridged by interstitial countercations and U6 clusters. Divalent transition metals (TM = MnII and ZnII) charge-balance and promote the fusion of 10 U6 and 10 U monomers into a wheel-shaped cluster (U70). Dissolution of U70 in organic media shows (by small-angle X-ray scattering) that differing supramolecular assemblies are accessed, controlled by TMII-linking of U70 clusters. Magnetic measurements of these assemblies reveal Curie–Weiss behavior at high temperatures, without pairing of the 5f2-electrons down to 2 K.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Oregon State Univ., Corvallis, OR (United States)
  2. Univ. of South Carolina, Columbia, SC (United States)
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States); Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1618851
Grant/Contract Number:  
NA0003763; SC0016574
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 142; Journal Issue: 19; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Colliard, Ian, Morrison, Gregory, Loye, Hans-Conrad zur, and Nyman, May. Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations. United States: N. p., 2020. Web. https://doi.org/10.1021/jacs.0c03041.
Colliard, Ian, Morrison, Gregory, Loye, Hans-Conrad zur, & Nyman, May. Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations. United States. https://doi.org/10.1021/jacs.0c03041
Colliard, Ian, Morrison, Gregory, Loye, Hans-Conrad zur, and Nyman, May. Wed . "Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations". United States. https://doi.org/10.1021/jacs.0c03041. https://www.osti.gov/servlets/purl/1618851.
@article{osti_1618851,
title = {Supramolecular Assembly of U(IV) Clusters and Superatoms with Unconventional Countercations},
author = {Colliard, Ian and Morrison, Gregory and Loye, Hans-Conrad zur and Nyman, May},
abstractNote = {Superatoms are nanometer-sized molecules or particles that form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in lattices of quantum dots, p-block clusters, and fullerenes. In this report, we introduce a family of uranium-oxysulfate cluster anions whose hierarchical assembly in water is controlled by two parameters: acidity and the lanthanide or transition-metal countercation. In acid, larger LnIII (Ln = La–Ho) link hexamer (U6) oxoclusters into body-centered cubic frameworks, while smaller LnIII (Ln = Er–Lu and Y) promote linking of 14 U6 clusters into hollow superclusters (U84 superatoms). U84 assembles into superlattices including cubic-closest packed, body-centered cubic, and interpenetrating networks, bridged by interstitial countercations and U6 clusters. Divalent transition metals (TM = MnII and ZnII) charge-balance and promote the fusion of 10 U6 and 10 U monomers into a wheel-shaped cluster (U70). Dissolution of U70 in organic media shows (by small-angle X-ray scattering) that differing supramolecular assemblies are accessed, controlled by TMII-linking of U70 clusters. Magnetic measurements of these assemblies reveal Curie–Weiss behavior at high temperatures, without pairing of the 5f2-electrons down to 2 K.},
doi = {10.1021/jacs.0c03041},
journal = {Journal of the American Chemical Society},
number = 19,
volume = 142,
place = {United States},
year = {2020},
month = {4}
}

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