Computational Insights into Iron Heterometal Installation in Polyoxovanadate-Alkoxide Clusters

Abstract

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 [VV 2VIV 3O5(μ 6-O)(μ 2-OCH3)12(FeIIICl)] polyoxovanadate-alkoxide cluster.