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

DM Brigham and AS Ivanov and BA Moyer and LH Delmau and VS Bryantsev and RJ Ellis, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 139, 17350-17358 (2017).

DOI: 10.1021/jacs.7b07318

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.

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