Photoelectron Spectroscopy and Theoretical Studies of Ge6MnO- Cluster with a MnV≡O Unit Interacting with a Double Aromatic Ge64- Ligand.

Abstract

The structures and chemical bonding of Ge6MnO- are investigated using anion photoelectron spectroscopy and theoretical calculations. The lowest energy structure of Ge6MnO- is found to have a C5v symmetric structure with an O atom attached to a pentagonal bipyramidal MnGe6. Chemical bonding analyses reveal that Ge6MnO- can be considered as a [MnV≡O]3+[Ge64-] complex with two unpaired 3d electrons on Mn. The Ge64- ligand is highly stable in Ge6MnO- and exhibits double aromaticity with 10 delocalized σ electrons and 6 delocalized π electrons. Our calculations show that the Ge64- ligand could also form [CrIV≡O]2+[Ge64-] in Na2Ge6CrO and [FeIV≡O]2+[Ge64-] in Na2Ge6FeO. The results suggest the possibility of designing and synthesizing a series of stable high-valent metal oxide anionic species with the composition [M≡O]n+[Ge64-] in the gas phase or in the salt-stabilized bulk solid materials.