Lattice Strains in the Ligand Framework in the Octahedral Metal Cluster Compounds as the Origin of Their Instability

The bond description for cluster compounds is commonly based on the molecular orbital diagrams, where the whole material is characterized by the specific electron population at various energetic levels. In contrast, this work is focused on the distribution of valence electrons between different liganding atoms, calculated first for a wide variety of octahedral metal cluster compounds (mainly Mo6 and Re6 chalcohalides) by the bond valence model. This distribution was found to be extremely nonuniform for most of the materials; it depends mostly on the ligand distances from the cluster center: The closer the ligand to the center, the higher is its charge (defined as its bond valence sum). To explain these results, a new model for the electrostatic interactions in the cluster compounds was proposed: The octahedral metal cluster with high polarizing power creates a strong electrostatic field, in which the adjacent separate anions behave as a part of a continuous dielectric medium, adjusting their charge to the...

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