Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides

Darren M. Driscoll; Hongjun Liu; Benjamin Reinhart; Ilja Popovs; Vera Bocharova; Santa Jansone-Popova; De En Jiang; Alexander S. Ivanov

doi:10.1021/acs.jpclett.2c03423

Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides

Darren M. Driscoll, Hongjun Liu, Benjamin Reinhart, Ilja Popovs, Vera Bocharova, Santa Jansone-Popova, De En Jiang, Alexander S. Ivanov

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

The role of counterions in molecular recognition of lanthanides is underexplored, especially when they exhibit weak interactions with the metal cations. Here, we report a complementary and comprehensive investigation integrating theoretical calculations with X-ray absorption fine structure spectroscopy, dynamic light scattering, and small-angle X-ray scattering to reveal atomic-scale structural features beyond the immediate coordination sphere of a system used for rare-earth element separations. Our results indicate the formation of an unusual T-shaped outer-sphere lanthanide complex, containing two ligands and two nitrate ions in the first coordination sphere, whereas the third nitrate is weakly coordinated and resides in the second shell. This unique structural arrangement causes inhomogeneous charge distribution, leading to self-assembly of the complexes into larger nanoclusters through sterically directed electrostatic interactions in the nonpolar medium. Our findings point to the importance of "noncoordinating"anions in defining the degree of supramolecular aggregation and ion cluster assembly.

Original language	English
Pages (from-to)	12076-12081
Number of pages	6
Journal	Journal of Physical Chemistry Letters
Volume	13
Issue number	51
DOIs	https://doi.org/10.1021/acs.jpclett.2c03423
State	Published - Dec 29 2022

Bibliographical note

Publisher Copyright:
© 2022 American Chemical Society.

Funding

This research was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Separation Science program and Materials Chemistry program under Award Number DE-SC00ERKCG21. This research used resources of the Advanced Photon Source at beamline 12-BM, a DOE User Facility, operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. This research used resources of the Computer and Data Environment for Science (CADES) at Oak Ridge National Laboratory (ORNL). Access to the Xeuss 3 SAXS/WAXS instrument was obtained via the ORNL instrumentation pool. The Xeuss 3 instrument was funded via the ORNL LDRD program. The manuscript was produced by UT-Battelle, LLC under Contract DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).

Funders	Funder number
ORNL LDRD	DE-AC05-00OR22725
Separation Science program and Materials Chemistry program	DE-SC00ERKCG21
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Argonne National Laboratory	DE-AC02-06CH11357

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title = "Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides",

abstract = "The role of counterions in molecular recognition of lanthanides is underexplored, especially when they exhibit weak interactions with the metal cations. Here, we report a complementary and comprehensive investigation integrating theoretical calculations with X-ray absorption fine structure spectroscopy, dynamic light scattering, and small-angle X-ray scattering to reveal atomic-scale structural features beyond the immediate coordination sphere of a system used for rare-earth element separations. Our results indicate the formation of an unusual T-shaped outer-sphere lanthanide complex, containing two ligands and two nitrate ions in the first coordination sphere, whereas the third nitrate is weakly coordinated and resides in the second shell. This unique structural arrangement causes inhomogeneous charge distribution, leading to self-assembly of the complexes into larger nanoclusters through sterically directed electrostatic interactions in the nonpolar medium. Our findings point to the importance of {"}noncoordinating{"}anions in defining the degree of supramolecular aggregation and ion cluster assembly.",

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AU - Driscoll, Darren M.

AU - Liu, Hongjun

AU - Reinhart, Benjamin

AU - Popovs, Ilja

AU - Bocharova, Vera

AU - Jansone-Popova, Santa

AU - Jiang, De En

AU - Ivanov, Alexander S.

PY - 2022/12/29

Y1 - 2022/12/29

N2 - The role of counterions in molecular recognition of lanthanides is underexplored, especially when they exhibit weak interactions with the metal cations. Here, we report a complementary and comprehensive investigation integrating theoretical calculations with X-ray absorption fine structure spectroscopy, dynamic light scattering, and small-angle X-ray scattering to reveal atomic-scale structural features beyond the immediate coordination sphere of a system used for rare-earth element separations. Our results indicate the formation of an unusual T-shaped outer-sphere lanthanide complex, containing two ligands and two nitrate ions in the first coordination sphere, whereas the third nitrate is weakly coordinated and resides in the second shell. This unique structural arrangement causes inhomogeneous charge distribution, leading to self-assembly of the complexes into larger nanoclusters through sterically directed electrostatic interactions in the nonpolar medium. Our findings point to the importance of "noncoordinating"anions in defining the degree of supramolecular aggregation and ion cluster assembly.

AB - The role of counterions in molecular recognition of lanthanides is underexplored, especially when they exhibit weak interactions with the metal cations. Here, we report a complementary and comprehensive investigation integrating theoretical calculations with X-ray absorption fine structure spectroscopy, dynamic light scattering, and small-angle X-ray scattering to reveal atomic-scale structural features beyond the immediate coordination sphere of a system used for rare-earth element separations. Our results indicate the formation of an unusual T-shaped outer-sphere lanthanide complex, containing two ligands and two nitrate ions in the first coordination sphere, whereas the third nitrate is weakly coordinated and resides in the second shell. This unique structural arrangement causes inhomogeneous charge distribution, leading to self-assembly of the complexes into larger nanoclusters through sterically directed electrostatic interactions in the nonpolar medium. Our findings point to the importance of "noncoordinating"anions in defining the degree of supramolecular aggregation and ion cluster assembly.

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Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides

Abstract

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