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Despite the importance of bulk lanthanide borides, nanoclusters of lanthanide and boron have rarely been investigated. Here we show that lanthanide–boron binary clusters, La 2 B x − , can form a new class of inverse-sandwich complexes, [Ln(η x -B x )Ln] − ( x = 7–9). Joint experimental and theoretical studies reveal that the monocyclic B x rings in the inverse sandwiches display similar bonding, consisting of three delocalized σ and three delocalized π bonds. Such monocyclic boron rings do not exist for bare boron clusters, but they are stabilized by the sandwiching lanthanide atoms. An electron counting rule is proposed to predict the sizes of the B x ring that can form stable inverse sandwiches. A unique (d-p)δ bond is found to play important roles in the stability of all three inverse-sandwich complexes.
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This content will become publicly available on December 4, 2025
Synthesis and Stability Phase Diagram of Topological Semimetal Family LnSb x Te 2–x–δ
The solid solution LnSbxTe2−x−δ (Ln = lanthanide) is a family of square-net topological semimetals that exhibit tunable charge density wave (CDW) distortions and band filling dependent on x, offering broad opportunities to examine the interplay of topological electronic states, CDW, and magnetism. While several Ln series have been characterized, gaps in the literature remain, inviting a systematic survey of the remaining composition space that is synthetically accessible. We present our efforts to synthesize LnSbxTe2−x−δ across the remaining lanthanides via chemical vapor transport. Compiling our results with the reported literature, we generate a stability phase diagram across the ranges of Ln and x. We find a stability boundary for intermediate x beyond Tb, while x = 1 and x = 0 can be isolated up to Ho and Dy, respectively. SEM and XRD analyses of unsuccessful reactions indicated the formation of several stable binary phases. The presence of structurally related LnTe3 in samples suggests that stability is limited by the size of Ln, due to increasing compressive strain along the layer stacking axis with decreasing size. Finally, we demonstrate that late Ln can be stabilized in LnSbxTe2−x−δ via substitution into larger Ln members, synthesizing La1−yHoySbxTe2−x−δ as a proof of concept.
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- Award ID(s):
- 2144295
- PAR ID:
- 10558402
- Publisher / Repository:
- Chemistry of Materials
- Date Published:
- Journal Name:
- Chemistry of Materials
- ISSN:
- 0897-4756
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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