Reconstructing a polyoxometalate decorated with zinc(II) complexes through a directional interactions approach

Hybrid polyoxometalate–metalorganic complexes have applications in catalysis, electronics, and biomedicine. The decavanadate (V₁₀) anion forms hybrid assemblies with transition-metal complexes through electrostatic and/or coordination interactions. However, the role of these interactions in driving the formation of V₁₀-based hybrids remains poorly understood. Herein, the hybrid complex [Zn(en)₂]₃[V₁₀O₂₈]·5H₂O, where en = C₂H₈N₂, containing two distinct zinc(II) coordination centers, was investigated using a theoretical approach aiming to elucidate the key interactions involved in its formation and stabilization. Zn(en)₂–OH₂ bonds and Zn(en)₂–O(V₁₀) contacts were compared, showing a greater stabilization of the Zn–V₁₀ assemblies, demonstrating that cooperative non-covalent contributions, particularly σ-hole interactions and hydrogen bonding, play a key role in the formation and stabilization of the hybrid structure, beyond the local covalent character of the metal–oxygen bond.