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  1. Abstract

    Despite its electron deficiency, boron can form multiple bonds with a variety of elements. However, multiple bonds between boron and main-group metal elements are relatively rare. Here we report the observation of boron-lead multiple bonds in PbB2Oand PbB3O2, which are produced and characterized in a cluster beam. PbB2Ois found to have an open-shell linear structure, in which the bond order of B☱Pb is 2.5, while the closed-shell [Pb≡B–B≡O]2–contains a B≡Pb triple bond. PbB3O2is shown to have a Y-shaped structure with a terminal B = Pb double bond coordinated by two boronyl ligands. Comparison between [Pb≡B–B≡O]2–/[Pb=B(B≡O)2]and the isoelectronic [Pb≡B–C≡O]/[Pb=B(C≡O)2]+carbonyl counterparts further reveals transition-metal-like behaviors for the central B atoms. Additional theoretical studies show that Ge and Sn can form similar boron species as Pb, suggesting the possibilities to synthesize new compounds containing multiple boron bonds with heavy group-14 elements.

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  2. null (Ed.)
    Size-selected negatively-charged boron clusters (B n − ) have been found to be planar or quasi-planar in a wide size range. Even though cage structures emerged as the global minimum at B 39 − , the global minimum of B 40 − was in fact planar. Only in the neutral form did the B 40 borospherene become the global minimum. How the structures of larger boron clusters evolve is of immense interest. Here we report the observation of a bilayer B 48 − cluster using photoelectron spectroscopy and first-principles calculations. The photoelectron spectra of B 48 − exhibit two well-resolved features at low binding energies, which are used as electronic signatures to compare with theoretical calculations. Global minimum searches and theoretical calculations indicate that both the B 48 − anion and the B 48 neutral possess a bilayer-type structure with D 2h symmetry. The simulated spectrum of the D 2h B 48 − agrees well with the experimental spectral features, confirming the bilayer global minimum structure. The bilayer B 48 −/0 clusters are found to be highly stable with strong interlayer covalent bonding, revealing a new structural type for size-selected boron clusters. The current study shows the structural diversity of boron nanoclusters and provides experimental evidence for the viability of bilayer borophenes. 
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