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As an electron-deficient element, boron possesses fascinating three-dimensional structures and unconventional chemical bonds. Nanoclusters of boron have also been found to exhibit intriguing structural properties, observed to have predominantly planar structures, in stark contrast to bulk boron allotropes, which are composed of the ubiquitous B₁₂icosahedral building blocks. Here, we report observation of the 2D-to-3D transition and bulk-like structural features in the size-selected boron clusters, as revealed by photoelectron spectroscopy, chemisorption experiments, and first-principles calculations. In the small to medium cluster size range, planar boron cluster anions are found to be unreactive and only B₄₆^–and B₅₆^–are observed to chemisorb C₂H₄and CO under ambient conditions, suggesting major structural transitions at these cluster sizes. Notably, B₅₆^–is also found to be able to chemisorb and activate CO₂. The global minimum of B₄₆^–is found to adopt a core-shell structure (B₂@B₄₄^–), consisting of a B₂core within a B₄₄shell, reminiscent of the interstitial B₂dumbbells in the high-pressureγ-B₂₈form of bulk boron. More remarkably, both the global minimum and the second most stable isomer of B₅₆^–exhibit nest-like configurations, featuring the iconic B₁₂icosahedral core surrounded by a B₄₄half-shell (B₁₂@h-B₄₄^–), signifying the onset of bulk-like structural characteristics in boron nanoclusters. 

Joint photoelectron spectroscopy and first-principles theory investigations indicate that the Pb-doped PbB₂(BO)_n⁻clusters (n= 0−2) undergo a transformation from σ + π doubly aromatic triangle PbB₂⁻to PbB₄(BO)₂^−/0complexes with a B≡B triple bond. 

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 PbB₂O^–and PbB₃O₂^–, which are produced and characterized in a cluster beam. PbB₂O^–is 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. PbB₃O₂^–is 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.