Observation of the Smallest Three‐Dimensional Neutral Boron Cluster

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 B9 cluster using threshold photoionization with a tunable vacuum ultraviolet free electron laser. The ionization potential of B9 is measured to be 8.45 ± 0.02 eV and it is found to have a heptagonal bipyramid D7h structure, 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 s and p bonding interactions within the B7 ring and between the B7 ring and the capping atoms. Photoionization of B9 breaks the single-electron B-B bond of the capping atoms, which undergo off-axis distortion to enhance interactions with the B7 ring in the singlet ground state of B9+. The single-electron B-B bond of the capping atoms appears to be crucial in stabilizing the D7h structure 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.