Co13O8-metalloxocubes: a new class of perovskite-like neutral clusters with cubic aromaticity

Exploring stable clusters to understand structural evolution from atoms to macroscopic matter and to construct new materials is interesting yet challenging in chemistry. Utilizing our newly developed deep-ultraviolet laser ionization mass spectrometry technique, here we observe the reactions of neutral cobalt clusters with oxygen and find a very stable cluster species of Co13O8 that dominates the mass distribution in the presence of a large flow rate of oxygen gas. The results of global-minimum structural search reveal a unique cubic structure and distinctive stability of the neutral Co13O8 cluster that forms a new class of metal oxides that we named as `metalloxo cubes'. Thermodynamics and kinetics calculations illustrate the structural evolution from icosahedral Co-13 to the metalloxocube Co13O8 with decreased energy, enhanced stability and aromaticity. This class of neutral oxygen-passivated metal clusters may be an ideal candidate for genetic materials because of the cubic nature of the building blocks and the stability due to cubic aromaticity.

Automated summary

Utilizing a newly developed deep-ultraviolet laser ionization mass spectrometry technique, reactions between neutral cobalt clusters and oxygen were observed, leading to the discovery of a very stable cluster species Co13O8 dominating the mass distribution in the presence of a large flow rate of oxygen gas. The global-minimum structural search revealed a unique cubic structure and distinctive stability of the neutral Co13O8 cluster, forming a new class of metal oxides termed as 'metalloxo cubes'. Thermodynamics and kinetics calculations illustrated the structural evolution from icosahedral Co-13 to metalloxocube Co13O8 with decreased energy, enhanced stability, and aromaticity. This class of neutral oxygen-passivated metal clusters may be ideal candidates for genetic materials due to the stability resulting from the cubic aromaticity of the building blocks.