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Snapshots of Ce70 Toroid Assembly from Solids and Solution

Cite this: J. Am. Chem. Soc. 2021, 143, 25, 9612–9621
Publication Date (Web):June 17, 2021
https://doi.org/10.1021/jacs.1c04095
Copyright © 2021 American Chemical Society
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    Abstract

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    Crystallization at the solid–liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [CeIV70(OH)36(O)64(SO4)60(H2O)10]4–, part of a larger emerging family of MIV70-materials (M = Zr, U, Ce), presents such an opportunity. We elucidated assembly mechanisms by the X-ray scattering (small-angle scattering and total scattering) of solutions and solids as well as crystallizing and identifying fragments of Ce70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce5, [Ce5(O)3(SO4)12]10-) and modular assembly from hexamer (Ce6) building units (Ce13, [Ce13(OH)6(O)12(SO4)14(H2O)14]6– and Ce62, [Ce62(OH)30(O)58(SO4)58]14-). Ce62, an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH4+, a structural motif not observed before in inorganic systems. The room temperature rapid assemblies of both Ce70 and Ce62, respectively, by the addition of Li+ and NH4+, along with ion-exchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c04095.

    • Details concerning synthesis, instrumentation, crystallography, crystallographic tables, summary of bond lengths and bond valence sum calculations, microscope images of crystals, ion-sorption studies, miscellaneous supplementary images, and table summarizing large cerium-oxo clusters synthesized to date (PDF)

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    CCDC 2057078, 2057085–2057086, 2057088–2057091, and 2064990 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 7 publications.

    1. Jonas Gosch, Erik Svensson Grape, Cesare Atzori, Felix Steinke, Kirill A. Lomachenko, A. Ken Inge, Norbert Stock. Solubility and Stability of Hexanuclear Ce(IV)–O Clusters. Chemistry of Materials 2023, 35 (15) , 5876-5885. https://doi.org/10.1021/acs.chemmater.3c00636
    2. Zhi-Kang Wang, Ming-Hao Du, Pierre Braunstein, Jian-Ping Lang. A Cut-to-Link Strategy for Cubane-Based Heterometallic Sulfide Clusters with Giant Third-Order Nonlinear Optical Response. Journal of the American Chemical Society 2023, 145 (18) , 9982-9987. https://doi.org/10.1021/jacs.3c01831
    3. Ian Colliard, Jessica C. Brown, May Nyman. Metal–Oxo Cluster Formation Using Ammonium and Sulfate to Differentiate MIV (Th, U, Ce) Chemistries. Inorganic Chemistry 2023, 62 (5) , 1891-1900. https://doi.org/10.1021/acs.inorgchem.2c01309
    4. Megan C. Wasson, Xingjie Wang, Patrick Melix, Selim Alayoglu, Andrew T. Y. Wolek, Ian Colliard, Florencia A. Son, Haomiao Xie, Eric Weitz, Timur Islamoglu, May Nyman, Randall Q. Snurr, Justin M. Notestein, Omar K. Farha. Interfacial Unit-Dependent Catalytic Activity for CO Oxidation over Cerium Oxysulfate Cluster Assemblies. ACS Applied Materials & Interfaces 2022, 14 (29) , 33515-33524. https://doi.org/10.1021/acsami.2c05937
    5. Xingjie Wang, Haomiao Xie, Julia G. Knapp, Megan C. Wasson, Yufang Wu, Kaikai Ma, Aaron E.B.S. Stone, Matthew D. Krzyaniak, Yijing Chen, Xuan Zhang, Justin M. Notestein, Michael R. Wasielewski, Omar K. Farha. Mechanistic Investigation of Enhanced Catalytic Selectivity toward Alcohol Oxidation with Ce Oxysulfate Clusters. Journal of the American Chemical Society 2022, 144 (27) , 12092-12101. https://doi.org/10.1021/jacs.2c02625
    6. Ming-Hao Du, Liu-Qing Chen, Lin-Peng Jiang, Wei-Dong Liu, La-Sheng Long, Lansun Zheng, Xiang-Jian Kong. Counterintuitive Lanthanide Hydrolysis-Induced Assembly Mechanism. Journal of the American Chemical Society 2022, 144 (12) , 5653-5660. https://doi.org/10.1021/jacs.2c01502
    7. Jennifer N. Wacker, Alexander S. Ditter, Samantha K. Cary, Aphra V. Murray, Jeffery A. Bertke, Gerald T. Seidler, Stosh A. Kozimor, Karah E. Knope. Reactivity of a Chloride Decorated, Mixed Valent CeIII/IV38–Oxo Cluster. Inorganic Chemistry 2022, 61 (1) , 193-205. https://doi.org/10.1021/acs.inorgchem.1c02705
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