Computational Insights into the Nucleation of Mixed-Valent Polyoxovanadate Alkoxide Clusters.

The synthesis of novel tunable electroactive species remains a key challenge for a wide range of chemical applications such as redox catalysis, energy storage, and optoelectronics. In recent years, polyoxovanadate (POV) alkoxide clusters have emerged as a new class of compounds with highly promising electrochemical applications. However, our knowledge of the formation pathways of POV alkoxides is rather limited. Understanding the speciation of POV alkoxides is fundamental for controlling and manipulating the evolution of transient species during their nucleation and therefore tuning the properties of the final product. Here, we present a computational study of the nucleation pathways of a mixed-valent [(VV6-nVIVnO6)(O)(O-CH3)12](4-n)+ POV alkoxide cluster in the absence of reducing agents other than methanol.