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Main Group Metal-Actinide Magnetic Coupling and Structural Response Upon U(4+) Inclusion Into Bi, Tl/Bi, or Pb/Bi
Niels Lichtenberger1, Robert J Wilson1, Armin R Eulenstein1
1Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg , Hans-Meerwein-Straße, 35043 Marburg, Germany.
Abstract:
The encapsulation of actinide ions in intermetalloid clusters has long been proposed but was never realized synthetically. We report the isolation and experimental, as well as quantum chemical, characterization of the uranium-centered clusters [U@Bi12](3-), [U@Tl2Bi11](3-), [U@Pb7Bi7](3-), and [U@Pb4Bi9](3-), upon reaction of (EE'Bi2)(2-) (E = Ga, Tl, E' = Bi; E = E' = Pb) and [U(C5Me4H)3] or [U(C5Me4H)3Cl] in 1,2-diaminoethane. For [U@Bi12](3-), magnetic susceptibility measurements rationalize an unprecedented antiferromagnetic coupling between a magnetic U(4+) site and a unique radical Bi12(7-) shell.
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