Cobalt-centred boron molecular drums with the highest coordination number in the CoB16- cluster.

Abstract

The electron deficiency and strong bonding capacity of boron have led to a vast variety of molecular structures in chemistry and materials science. Here we report the observation of highly symmetric cobalt-centered boron drum-like structures of CoB16(-), characterized by photoelectron spectroscopy and ab initio calculations. The photoelectron spectra display a relatively simple spectral pattern, suggesting a high symmetry structure. Two nearly degenerate isomers with D8d (I) and C4v (II) symmetries are found computationally to compete for the global minimum. These drum-like structures consist of two B8 rings sandwiching a cobalt atom, which has the highest coordination number known heretofore in chemistry. We show that doping of boron clusters with a transition metal atom induces an earlier two-dimensional to three-dimensional structural transition. The CoB16(-) cluster is tested as a building block in a triple-decker sandwich, suggesting a promising route for its realization in the solid state.