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Trefoil-shaped outer-sphere ion clusters mediate lanthanide(III) ion transport with diglycolamide ligands...

Publication Type
Journal
Journal Name
Journal of the American Chemical Society
Publication Date
Page Numbers
17350 to 17358
Volume
139
Issue
48

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.