Computational Insights into Iron Heterometal Installation in Polyoxovanadate-Alkoxide Clusters.

Polyoxovanadate-alkoxide clusters are a new class of electroactive species with applications in a wide variety of fields from redox catalysis to energy storage. Heterometallic installation in these species can be used to modulate the redox properties of polyoxovanadate-alkoxide clusters and thus their applications. However, the formation mechanism of heterometallic polyoxovanadate alkoxides during the solvothermal process is unknown, limiting our understanding regarding what thermodynamic driving forces and/or kinetic barriers are present in the heterometal insertion. Here, we present a computational study on the nucleation pathways of the iron-functionalized mixed-valent hexameric [V V 2 V IV 3 O 5 (μ 6 -O)(μ 2 -OCH 3 ) 12 (Fe III Cl)] polyoxovanadate-alkoxide cluster.