Boron-based nanoclusters have unique structures, bonding, and dynamic properties, which originate from boron's electron-deficiency. We demonstrate here that pouring in extra electrons can alter such systems fundamentally. A coaxial triple-layered Be6B102 sandwich cluster is designed via global structural searches and quantum chemical calculations. It is well defined as the global minimum, which consists of a slightly elongated B10 monocyclic ring and two Be3 rings, the latter forming a Be6 trigonal-prism albeit without interlayer Be–Be bonding. The B10 ring shows structural and chemical integrity with respect to the Be3 rings, and yet it differs markedly from the free B10 cluster and closely
resembles the C10 cluster. The present data testify to the idea of electronic transmutation, in which a B is equivalent to C and a B10 cluster, upon charge-transfer, is converted to and stabilized as a monocyclic ring analogous to C10. Chemical bonding analyses reveal that the B10 ring in the Be6B102 cluster has 10p and 10s delocalization and each Be3 ring is held together by 2s electrons, collectively rendering
four-fold p/s aromaticity. The bonding pattern is in line with the formula of [Be3]4+[B10]10[Be3]4+, suggesting a highly charged electron-transfer complex. Furthermore, the Be6B102 cluster is dynamically fluxional with dual modes of revolution (orbiting) and rotation (twisting), being structurally robust at least up to a temperature of 1500 K.
