Main Group Metal-Actinide Magnetic Coupling and Structural Response Upon U(4+) Inclusion Into Bi, Tl/Bi, or Pb/Bi Cages.

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.

DOI: 10.1021/jacs.6b04363

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Cite this paper

@article{Lichtenberger2016MainGM, title={Main Group Metal-Actinide Magnetic Coupling and Structural Response Upon U(4+) Inclusion Into Bi, Tl/Bi, or Pb/Bi Cages.}, author={Niels Lichtenberger and Robert J. Wilson and Armin Rainer Eulenstein and W erner Massa and Rodolphe Cl{\'e}rac and Florian Weigend and Stefanie Dehnen}, journal={Journal of the American Chemical Society}, year={2016}, volume={138 29}, pages={9033-6} }