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Abstract The discovery of borospherenes unveiled the capacity of boron to form fullerene-like cage structures. While fullerenes are known to entrap metal atoms to form endohedral metallofullerenes, few metal atoms have been observed to be part of the fullerene cages. Here we report the observation of a class of remarkable metallo-borospherenes, where metal atoms are integral parts of the cage surface. We have produced La₃B₁₈^–and Tb₃B₁₈^–and probed their structures and bonding using photoelectron spectroscopy and theoretical calculations. Global minimum searches revealed that the most stable structures of Ln₃B₁₈^–are hollow cages withD_3hsymmetry. The B₁₈-framework in the Ln₃B₁₈^–cages can be viewed as consisting of two triangular B₆motifs connected by three B₂units, forming three shared B₁₀rings which are coordinated to the three Ln atoms on the cage surface. These metallo-borospherenes represent a new class of unusual geometry that has not been observed in chemistry heretofore. 

Abstract Despite major progress in the investigation of boron cluster anions, direct experimental study of neutral boron clusters remains a significant challenge because of the difficulty in size selection. Here we report a size‐specific study of the neutral B₉cluster using threshold photoionization with a tunable vacuum ultraviolet free electron laser. The ionization potential of B₉is measured to be 8.45±0.02 eV and it is found to have a heptagonal bipyramidD_7hstructure, quite different from the planar molecular wheel of the B₉^‐anionic cluster. Chemical bonding analyses reveal superior stability of the bipyramidal structure arising from delocalized σ and π bonding interactions within the B₇ring and between the B₇ring and the capping atoms. Photoionization of B₉breaks the single‐electron B‐B bond of the capping atoms, which undergo off‐axis distortion to enhance interactions with the B₇ring in the singlet ground state of B₉⁺. The single‐electron B‐B bond of the capping atoms appears to be crucial in stabilizing theD_7hstructure of B₉. This work opens avenues for direct size‐dependent experimental studies of a large variety of neutral boron clusters to explore the stepwise development of network structures.