Expanded Inverse-Sandwich Complexes of Lanthanum Borides: La2B10 – and La2B11

Inverse-sandwich structures have been observed recently for dilanthanide boride clusters, in which two Ln atoms sandwich a monocyclic B x ring for x = 7–9. An interesting question is if larger B x rings are possible to form such inverse-sandwich clusters. Here we address this question by investigati...

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Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2021-04, Vol.125 (12), p.2622-2630
Main Authors: Jiang, Zhi-Yu, Chen, Teng-Teng, Chen, Wei-Jia, Li, Wan-Lu, Li, Jun, Wang, Lai-Sheng
Format: Article
Language:English
Subjects:
A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
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Summary:Inverse-sandwich structures have been observed recently for dilanthanide boride clusters, in which two Ln atoms sandwich a monocyclic B x ring for x = 7–9. An interesting question is if larger B x rings are possible to form such inverse-sandwich clusters. Here we address this question by investigating La2B10 – and La2B11 – using photoelectron spectroscopy and ab initio quantum chemical calculations. Photoelectron spectra of La2B10 – and La2B11 – show complicated, but well-resolved, spectral features that are used to compare with theoretical calculations. We have found that global minimum structures of the two clusters are based on the octa-boron ring. The global minimum of La2B10 – consists of two chiral enantiomers with C 1 symmetry, which can be viewed as adding a B2 unit off-plane to the B8 ring, whereas that of La2B11 – can be viewed as adding a B3 unit in-plane to the B8 ring in a second coordination shell. Chemical bonding analyses reveal localized B–B bonds on the edge of the clusters and delocalized bonds in the expanded boron frameworks. The interactions between the La atoms and the boron frameworks include the unique (d–p)­δ bonding, which was found to be the key for inverse-sandwich complexes with monocyclic boron rings. The current study confirms that the largest monocyclic boron ring to form the inverse-sandwich structures is B9 and provide insights into the structural evolutions of larger lanthanide boride clusters.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.1c01149