Speciation of Mixed-Valent Polyoxovanadate-Alkoxide Clusters (POV-Alkoxides)

The design and synthesis of tunable electroactive molecules which has wide applications as catalysts, actuators, and sensors remains one of the key challenges in synthetic chemistry. Polyoxovanadate-alkoxide clusters (POV-alkoxides) have emerged as a new class of compounds with the essential electronic and physical properties that are required for an ideal redox active material. However, the controlled synthesis of these POV-alkoxides clusters for tuning their electronic property are still an underdeveloped field largely due to lack of mechanistic insight of POV-alkoxides formation. Here, we are conducting computational researches on the speciation of a mixed-valent [V6O7(OCH3)12] POV-alkoxide clusters that can be functionalized to a redox reservoir by incorporating heterometallic species. This speciation study explores both sequential step wise cluster formation and self-assembly of trimer [VV3O3(OCH3)9] and trimer intermediate [VIV3O4(OCH3)6], [VV3O4(OCH3)9]2- for cluster formation. Our calculation shows that cluster formation through the self-assembly of building blocks favors over the sequential cluster growth of hexamer from pentamer, pentamer from tetramer and so on. Moreover, cluster containing VIV are thermodynamically more favorable compare to the clusters which has only VV. Here we will present the DFT mechanistic study of [V6O7(OCH3)12]mixed-valent POV-alkoxide cluster formation considering effect of temperature, pressure, presence of methoxy anion and reducing agent in solution as well as effect of vanadium oxidation state for the stability of clusters