Trefoil-Shaped Outer-Sphere Ion Clusters Mediate Lanthanide(III) Ion Transport with Diglycolamide Ligands

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Abstract

Outer-sphere ion clusters are inferred in many important natural and technological processes, but their mechanisms of assembly and solution structures are difficult to define. Here, we characterize trefoil-shaped outer-sphere lanthanide chloride and nitrate ion clusters in hydrocarbon solutions formed during liquid-liquid extraction with diglycolamide ligands. These are assembled through steric and electrostatic forces, where the anions reside in equidistant "clefts" between coordinating diglycolamide ligands in positions that satisfy both repulsive and attractive ion-ion interactions. Our study shows how sterically directed electrostatic interactions may assemble stable outer-sphere ion clusters in organic solutions, elucidating new strategies for controlling ion cluster assembly and extraction.

Original languageEnglish
Pages (from-to)17350-17358
Number of pages9
JournalJournal of the American Chemical Society
Volume139
Issue number48
DOIs
StatePublished - Dec 6 2017

Funding

The authors thank Mark R. Antonio (a.k.a. “The MAntonio”) for very useful discussions on the EXAFS data fitting. D.M.B., B.A.M., L.H.D., and R.J.E were supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office. A.S.I. and V.S.B. were supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357.

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