Probing the electronic structure of the CoB16− drum complex: Unusual oxidation state of Co−1

Abstract

Since the discovery of the first drum-like CoB16− complex, metal-doped drum-like boron nanotubular structures have been investigated with various metal dopants and different tubular size, forming a new class of novel nanostructures. The CoB16− cluster was found to be composed of a central Co atom coordinated by two fused B8 rings in a tubular structure, representing the potential embryo of metal-filled boron nanotubes and providing opportunities to design one-dimensional metal-boron nanostructures. Here we report improved photoelectron spectroscopy and a more in-depth electronic structure analysis of CoB16−, providing further insight into the chemical bonding and stability of the drum-like doped boron tubular structures. Most interestingly, we find that the central Co atom has an unusually low oxidation state of −1 and neutral CoB16 can be viewed as a charge transfer complex (Co−@B16+), suggesting both covalent and electrostatic interactions between the dopant and the boron drum.