Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides

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

doi:10.1021/acs.jpclett.2c03423

Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides

Journal Article · Thu Dec 22 00:00:00 EST 2022 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.2c03423· OSTI ID:2377432

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Univ. of California, Riverside, CA (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

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. Here, 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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Compute and Data Environment for Science (CADES)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725

OSTI ID:: 2377432

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 51 Vol. 13; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Noncoordinating Secondary Sphere Ion Modulates Supramolecular Clustering of Lanthanides

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