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Monovalent lanthanide(I) in borozene complexes

Wan-Lu Li, Teng-Teng Chen, Wei-Jia Chen, Jun Li () and Lai-Sheng Wang ()
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Wan-Lu Li: Tsinghua University
Teng-Teng Chen: Brown University
Wei-Jia Chen: Brown University
Jun Li: Tsinghua University
Lai-Sheng Wang: Brown University

Nature Communications, 2021, vol. 12, issue 1, 1-9

Abstract: Abstract Lanthanide (Ln) elements are generally found in the oxidation state +II or +III, and a few examples of +IV and +V compounds have also been reported. In contrast, monovalent Ln(+I) complexes remain scarce. Here we combine photoelectron spectroscopy and theoretical calculations to study Ln-doped octa-boron clusters (LnB8−, Ln = La, Pr, Tb, Tm, Yb) with the rare +I oxidation state. The global minimum of the LnB8− species changes from Cs to C7v symmetry accompanied by an oxidation-state change from +III to +I from the early to late lanthanides. All the C7v-LnB8− clusters can be viewed as a monovalent Ln(I) coordinated by a η8-B82− doubly aromatic ligand. The B73−, B82−, and B9− series of aromatic boron clusters are analogous to the classical aromatic hydrocarbon molecules, C5H5−, C6H6, and C7H7+, respectively, with similar trends of size and charge state and they are named collectively as “borozenes”. Lanthanides with variable oxidation states and magnetic properties may be formed with different borozenes.

Date: 2021
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DOI: 10.1038/s41467-021-26785-9

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